Tethered Alkylidyne and Methods of Making the Same

Abstract

Provided herein are compounds that can be used as a catalyst to form cyclic polymers, and methods of making and using the same. For example, provided herein are compounds of formula (I), and formula (1-dimer).

##STR00001##

Claims

1. A compound having a structure represented by formula (I) or formula (I-dimer): ##STR00025## wherein the dashed lines are optional double bonds; M is a transition metal; L is a neutral or anionic ligand; each L is independently absent or a neutral or anionic ligand; Q is selected from S, O, N, NR.sup.5, N(R.sup.5).sub.2, P(R.sup.6).sub.2, C, CR.sup.7, C(R.sup.7).sub.2, BR.sup.8, Si(R.sup.9).sub.2, Se, and Te; X is selected from a bond, S, O, N, NR.sup.5, Se, Te, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.4-C.sub.10cycloalkyl, Ar.sup.1, C.sub.1-C.sub.4heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; R.sup.3 is selected from a bond, C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2C (R.sup.1).sub.2, and C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2; each R.sup.1 is independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two geminal R.sup.1 together with the carbon atom to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; each R.sup.2 is independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or both R.sup.2 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; each R.sup.6 and R.sup.9 are independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.5, two vicinal R.sup.6, two vicinal R.sup.8, or two vicinal R.sup.9, together with the atoms to which they are attached, form a five- to eight-member cycloalkyl, aryl, heteroaryl, or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; each R.sup.5, R.sup.7, and R.sup.8 are independently selected from H, C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.7 together with the atoms to which they are attached, form a five- to eight-member cycloalkyl, aryl, heteroaryl, or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; and, each Ar.sup.1 is independently selected from C.sub.6-C.sub.22 aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S.

2. The compound of claim 1, wherein M is selected from Cr, Mo, W, Fe, Ru, Rh, Ir, and Os.

3. (canceled)

4. The compound of claim 1, wherein Q is selected from S, O, N, NR.sup.5, P(R.sup.6).sub.2, C, CR.sup.7, C(R.sup.7).sub.2, and BR.sup.8.

5. (canceled)

6. The compound of claim 1, wherein X is selected from O, NR.sup.5, C.sub.4-C.sub.10cycloalkyl, Ar.sup.1 or C.sub.1-C.sub.8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S.

7. The compound of claim 1, wherein X is ##STR00026##

8. The compound of claim 1, wherein each R.sup.1 is independently selected from H, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20haloalkyl, C.sub.4-C.sub.20cycloalkyl, or Ar.sup.1.

9. The compound of claim 8, wherein at least one R.sup.1 is H, C.sub.1-C.sub.5haloalkyl, C.sub.1-C.sub.6alkyl or C.sub.4-C.sub.8cycloalkyl, or Ar.sup.1.

10. (canceled)

11. (canceled)

12. The compound of claim 1, wherein each R.sup.2 is independently selected from H, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20haloalkyl, C.sub.4-C.sub.20cycloalkyl, or Ar.sup.1.

13. The compound of claim 12, wherein at least one R.sup.2 is H, C.sub.1-C.sub.5haloalkyl, C.sub.1-C.sub.6alkyl or C.sub.4-C.sub.8cycloalkyl, or Ar.sup.1.

14. (canceled)

15. (canceled)

16. The compound of claim 1, wherein R.sup.3 is C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2, or C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2.

17. (canceled)

18. The compound of claim 1, wherein L comprises one or more functional groups selected from the group of amine, amide, imide, phosphine, phosphite, phosphinite, phosphonite, N-heterocyclic carbene, hydroxyl, oxo, alkoxide, aryloxide, thiol, alkylthiol, arylthiol, carbene, alkyl, cycloalkyl, aryl, heteroaryl, and heterocycloalkyl.

19. (canceled)

20. The compound of claim 1, wherein L is selected from the group of N(R.sup.5).sub.2, N(R.sup.5), OR.sup.10, SR.sup.11, O, S, OS(O.sub.2)CF.sub.3, carbene, N-heterocyclic carbene, C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R.sup.10 and R.sup.11 are independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S.

21. (canceled)

22. The compound of claim 1, wherein each L is independently absent or comprises one or more functional groups selected from the group of amine, amide, imide, phosphine, phosphite, phosphinite, phosphonite, N-heterocyclic carbene, hydroxyl, oxo, alkoxide, aryloxide, thiol, alkylthiol, arylthiol, carbene, alkyl, cycloalkyl, aryl, heteroaryl, and heterocycloalkyl.

23. (canceled)

24. (canceled)

25. The compound of claim 22, wherein each L is independently selected from the group of N(R.sup.5).sub.3, N(R.sup.5).sub.2, N(R.sup.5), O(R.sup.10).sub.2, OR.sup.10, S(R.sup.11).sub.2, SR.sup.11, N-heterocyclic carbene, C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, C.sub.4-C.sub.8heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R.sup.10 and R.sup.11 are independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two R.sup.10 together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand.

26. (canceled)

27. The compound of claim 1, selected from the group of: ##STR00027##

28. A method of preparing the compound of formula (I) according to claim 1, the method comprising: admixing a compound of formula (II) and a compound of formula (III) to form a compound of formula (IV), or formula (IV-dimer); and, admixing the compound of formula (IV), or formula (IV-dimer) with a deprotonating agent to form the compound of formula (I): ##STR00028## wherein the dashed lines are optional double bonds; M is a transition metal; L.sup.a and L.sup.b are neutral or anionic ligands; each L.sup.a is independently absent or a neutral or anionic ligand; each L.sup.b is independently absent or a neutral or anionic ligand; Q.sup.a and Q.sup.b are selected from S, O, N, NR.sup.5a, N(R.sup.5a).sub.2, P(R.sup.6a).sub.2, C, CR.sup.7a, C(R.sup.7a).sub.2, BR.sup.8a, Si(R.sup.9a).sub.2, Se, and Te; Z is selected from H, halo, or a counterion for Q.sup.a; X.sup.a and X.sup.b are selected from S, O, N, NR.sup.5a, Se, Te, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.4-C.sub.10cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.4heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; R.sup.3a and R.sup.3b are selected from a bond, C(R.sup.1a).sub.2, C(R.sup.1a).sub.2C(R.sup.1a).sub.2, C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2, C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2, and C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2; each R.sup.1a and R.sup.1b are independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, two geminal R.sup.1a or R.sup.1b together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.1a or R.sup.1b together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; each R.sup.2a and R.sup.2b is independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or both R.sup.2a or R.sup.2b together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; each R.sup.5a, R.sup.6a, R.sup.7a, R.sup.8a and R.sup.9a is independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.5a, two vicinal R.sup.6a, two vicinal R.sup.7a, two vicinal R.sup.8a, or two vicinal R.sup.9a, together with the atoms to which they are attached, form a five- to eight-member cycloalkyl, aryl, heteroaryl, or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; each Ar.sup.1a is independently selected from C.sub.6-C.sub.22 aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S.

29.-69. (canceled)

70. A method of preparing a cyclic polymer, the method comprising: admixing a plurality of alkene monomers, alkyne monomers, or both in the presence of the compound of formula (I) according to claim 1 to polymerize the plurality of alkene monomers, alkyne monomers, or both to form the cyclic polymer.

71.-79. (canceled)

80. A cyclic polymer prepared according to the method of claim 70.

81. A cyclic polymer having a structure according to formula (V): ##STR00029## wherein the dashed line is an optional double or triple bond; each R.sup.12 is independently absent, H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C.sub.1-C.sub.20alkoxy, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.12 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl, heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, aryl, or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S; and n is an integer of at least 2.

82. The cyclic polymer of claim 81 having a structure according to formula (VI): ##STR00030## wherein the dashed line is an optional double or triple bond; each R.sup.12 is independently absent, H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C.sub.1-C.sub.20alkoxy, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.12 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl, heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, aryl, or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S; each R.sup.13 is independently selected from, H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C.sub.1-C.sub.20alkoxy, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.4-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; and n is an integer of at least 2.

83. (canceled)

Description

BRIEF DESCRIPTION OF DRAWINGS

[0044] FIG. 1 is a reaction scheme for the preparation of a ligand for a compound of formula (I), or dimer thereof, of the disclosure.

[0045] FIG. 2 is a 1-D NOESY/EXSY spectrum of W(CCH.sub.2CH.sub.2C.sub.6H.sub.4-o-CH.sub.2O)(CH.sup.tBu)(O-2,6-.sup.iPr.sup.2C.sub.6H.sub.3) (C.sub.6D.sub.6, 500 MHz, 25? C.).

[0046] FIG. 3 is the molecular structure of a catalyst of the disclosure, with non-carbon atoms labelled, and having ligand and solvent disorder parts and hydrogen atoms removed for clarity.

[0047] FIG. 4 is a stacked .sup.1H NMR spectrum of W(CCH.sub.2CH.sub.2C.sub.6H.sub.4-o-CH.sub.2O)(CH.sup.tBu)(O-2,6-.sup.iPr.sub.2C.sub.6H.sub.3), (bottom), 3,8-didodecyloxy-5,6-dihydro-11,12-didehydrodibenzo[a,e]-[8]annulen (2nd), and polymerization progress (top 3 spectra).

[0048] FIG. 5 is a plot of the log of molecular weight versus elution volume for linear and cyclic poly-(o-phenylene ethynylene) formed according to an embodiment of the invention (Run 1).

[0049] FIG. 6 is a plot of the log of molecular weight versus elution volume for linear and cyclic poly-(o-phenylene ethynylene) formed according to an embodiment of the invention (Run 2).

[0050] FIG. 7 is a plot of log (intrinsic viscosity) vs log (viscosity-average molar mass) for linear and cyclic poly-(o-phenylene ethynylene) formed according to an embodiment of the invention (Run 1).

[0051] FIG. 8 is a plot of log (intrinsic viscosity) vs log (viscosity-average molar mass) for linear and cyclic poly-(o-phenylene ethynylene) formed according to an embodiment of the invention (Run 2).

[0052] FIG. 9 is a plot of <R.sub.g.sup.2> vs molar mass for linear and cyclic poly-(o-phenylene ethynylene) formed according to an embodiment of the invention, where <R.sub.g.sup.2> is the mean square radius (Run 1).

[0053] FIG. 10 is a plot of <R.sub.g.sup.2> vs molar mass for linear and cyclic poly-(o-phenylene ethynylene) formed according to an embodiment of the invention, where <R.sub.g.sup.2> is the mean square radius (Run 2).

DETAILED DESCRIPTION

[0054] Provided herein are compounds having a structure represented by formulas (I), (II), (III), (IV), (V), and (VI), and methods of making and using said compounds. In embodiments, compounds having a structure represented by formulas (I) and (IV) can be in the form of a dimer. Compounds having a structure represented by formula (I), and dimers thereof, can be used as a catalyst in the preparation of cyclic polymers. Advantageously, compounds having a structure represented by formula (I), or dimers thereof, can generate high-molecular weight cyclic polyalkynes.

[0055] The compounds of the disclosure have structures represented by formulas (I), (II), (III), (IV), (V), and (VI) and these compounds may also be referred to as compounds of formula (I), compounds of formula (II), compounds of formula (III), compounds of formula (IV), compounds of formula (V), and compounds of formula (VI), herein, respectively.

[0056] Modifications and other embodiments will come to mind to one skilled in the art to which the disclosed compositions and methods pertain having the benefit of the teachings presented herein and the associated drawings. Therefore, it is to be understood that the disclosures are not to be limited to the specific embodiments disclosed and that modifications and other embodiments are intended to be included within the scope of the appended claims.

[0057] It is also to be understood that the terminology used herein is for the purpose of describing particular aspects only and is not intended to be limiting. As used in the specification and in the claims, the term comprising can include the aspect of consisting of. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which the disclosed compositions and methods belong. In this specification and in the claims which follow, reference will be made to a number of terms which shall be defined herein.

[0058] As will be apparent to those of skill in the art upon reading this disclosure, each of the individual embodiments described and illustrated herein has discrete components and features which may be readily separated from or combined with the features of any of the other several embodiments without departing from the scope or spirit of the present disclosure. Any recited method can be carried out in the order of events recited or in any other order that is logically possible.

Definitions

[0059] As used herein, the term alkyl refers to straight chained and branched saturated hydrocarbon groups containing one to thirty carbon atoms, for example, one to twenty two carbon atoms, or one to twenty carbon atoms, or one to ten carbon atoms. The term C.sub.n means the alkyl group has n carbon atoms. For example, C.sub.4 alkyl refers to an alkyl group that has 4 carbon atoms. C.sub.1-20alkyl and C.sub.1-C.sub.20 alkyl refer to an alkyl group having a number of carbon atoms encompassing the entire range (i.e., 1 to 20 carbon atoms), as well as all subgroups (e.g., 1-20, 2-15, 1-10, 5-12, 1, 2, 3, 4, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, and 20 carbon atoms). Nonlimiting examples of alkyl groups include, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl (2-methylpropyl), t-butyl (1,1-dimethylethyl), 3,3-dimethylpentyl, and 2-ethylhexyl. Unless otherwise indicated, an alkyl group can be an unsubstituted alkyl group or a substituted alkyl group. Unless otherwise indicated, an alkyl group can be an unsubstituted alkyl group or a substituted alkyl group. A specific substitution on an alkyl can be indicated by inclusion in the term, e.g., haloalkyl indicates an alkyl group substituted with one or more (e.g., one to 10) halogens.

[0060] As used herein, the term heteroalkyl is defined similarly as alkyl except that the straight chained and branched saturated hydrocarbon group contains, in the alkyl chain, one to five heteroatoms independently selected from oxygen (O), nitrogen (N), and sulfur(S). In particular, the term heteroalkyl refers to a saturated hydrocarbon containing one to twenty carbon atoms and one to five heteroatoms. In general, in embodiments wherein the heteroalkyl is provided as a substituent, the heteroalkyl is bound through a carbon atom, e.g., a heteroalkyl is distinct from an alkoxy or amino group.

[0061] As used herein, the term cycloalkyl refers to an aliphatic cyclic hydrocarbon group containing four to twenty carbon atoms, for example, four to fifteen carbon atoms, or four to ten carbon atoms (e.g., 4, 5, 6, 7, 8, 10, 12, 14, 15, 16, 17, 18, 19 or 20 carbon atoms). The term C.sub.n means the cycloalkyl group has n carbon atoms. For example, C.sub.5 cycloalkyl refers to a cycloalkyl group that has 5 carbon atoms in the ring. C.sub.5-8 cycloalkyl and C.sub.5-C.sub.8 cycloalkyl refer to cycloalkyl groups having a number of carbon atoms encompassing the entire range (i.e., 5 to 8 carbon atoms), as well as all subgroups (e.g., 5-6, 6-8, 7-8, 5-7, 5, 6, 7, and 8 carbon atoms). Nonlimiting examples of cycloalkyl groups include cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, and cyclooctyl. Unless otherwise indicated, a cycloalkyl group can be an unsubstituted cycloalkyl group or a substituted cycloalkyl group. The cycloalkyl groups described herein can be isolated or fused to another cycloalkyl group, a heterocycloalkyl group, an aryl group and/or a heteroaryl group, or a bicyclic group or a tricyclic group. For example, the cycloalkyl groups described herein can be a cyclohexyl fused to another cyclohexyl, or an adamantyl.

[0062] As used herein, the term heterocycloalkyl is defined similarly as cycloalkyl, except the ring contains one to five heteroatoms independently selected from oxygen, nitrogen, and sulfur. In particular, the term heterocycloalkyl refers to a ring containing a total of five to twenty atoms, for example three to fifteen atoms, or three to ten atoms, of which 1, 2, 3, 4, or 5 of those atoms are heteroatoms independently selected from the group consisting of oxygen, nitrogen, and sulfur, and the remaining atoms in the ring are carbon atoms. Nonlimiting examples of heterocycloalkyl groups include piperidine, tetrahydrofuran, tetrahydropyran, dihydrofuran, morpholine, and the like. The heterocycloalkyl groups described herein can be isolated or fused to another heterocycloalkyl group, a cycloalkyl group, an aryl group, and/or a heteroaryl group. In some embodiments, the heterocycloalkyl groups described herein comprise one oxygen ring atom (e.g., oxiranyl, oxetanyl, tetrahydrofuranyl, and tetrahydropyranyl).

[0063] As used herein, the term alkenyl is defined identically as alkyl, except for containing at least one carbon-carbon double bond, and having two to thirty carbon atoms, for example, two to twenty carbon atoms, or two to ten carbon atoms. The term C.sub.n means the alkenyl group has n carbon atoms. For example, C.sub.4 alkenyl refers to an alkenyl group that has 4 carbon atoms. C.sub.2-7 alkenyl and C.sub.2-C.sub.7 alkenyl refer to an alkenyl group having a number of carbon atoms encompassing the entire range (i.e., 2 to 7 carbon atoms), as well as all subgroups (e.g., 2-6, 2-5, 3-6, 2, 3, 4, 5, 6, and 7 carbon atoms). Specifically contemplated alkenyl groups include ethenyl, 1-propenyl, 2-propenyl, and butenyl. Unless otherwise indicated, an alkenyl group can be an unsubstituted alkenyl group or a substituted alkenyl group.

[0064] As used herein, the term aryl refers to monocyclic or polycyclic (e.g., fused bicyclic and fused tricyclic) carbocyclic aromatic ring systems having six to twenty carbon atoms, for example six to fifteen carbon atoms or six to ten carbon atoms. The term C.sub.n means the aryl ring structure has n carbon atoms and does not include carbons atoms in a substituent. For example, C.sub.6 aryl refers to an aryl group that has 6 carbon atoms in the ring. Examples of aryl groups include, but are not limited to, phenyl, naphthyl, tetrahydronaphthyl, phenanthrenyl, biphenylenyl, indanyl, indenyl, anthracenyl, and fluorenyl. Unless otherwise indicated, an aryl group can be an unsubstituted aryl group or a substituted aryl group.

[0065] As used herein, the term heteroaryl refers to a cyclic aromatic ring system having five to twenty total ring atoms (e.g., a monocyclic aromatic ring with 5-6 total ring atoms), of which 1, 2, 3, 4, or 5 of those atoms are heteroatoms independently selected from the group consisting of oxygen, nitrogen, and sulfur, and the remaining atoms in the ring are carbon atoms. Unless otherwise indicated, a heteroaryl group can be unsubstituted or substituted with one or more, and in particular one to four, substituents selected from, for example, halo, alkyl, alkenyl, OCF.sub.3, NO.sub.2, CN, NC, OH, alkoxy, amino, CO.sub.2H, CO.sub.2alkyl, aryl, and heteroaryl. In some cases, the heteroaryl group is substituted with one or more of alkyl and alkoxy groups. Heteroaryl groups can be isolated (e.g., pyridyl) or fused to another heteroaryl group (e.g., purinyl), a cycloalkyl group (e.g., tetrahydroquinolinyl), a heterocycloalkyl group (e.g., dihydronaphthyridinyl), and/or an aryl group (e.g., benzothiazolyl and quinolyl). Examples of heteroaryl groups include, but are not limited to, thienyl, furyl, pyridyl, pyrrolyl, oxazolyl, quinolyl, thiophenyl, isoquinolyl, indolyl, triazinyl, triazolyl, isothiazolyl, isoxazolyl, imidazolyl, benzothiazolyl, pyrazinyl, pyrimidinyl, thiazolyl, and thiadiazolyl. When a heteroaryl group is fused to another heteroaryl group, then each ring can contain five to twenty total ring atoms and one to five heteroatoms in its aromatic ring.

[0066] As used herein, the term hydroxy or hydroxyl refers to the OH group. As used herein, the term thiol refers to the SH group.

[0067] As used herein, the term alkoxy or alkoxyl refers to a O-alkyl group. As used herein, the term aryloxy or aryloxyl refers to a O-aryl group. As used herein, the term heteroaryloxy or heteroaryloxyl refers to a O-heteroaryl group.

[0068] As used herein, the term alkylthio refers to a S-alkyl group. As used herein, the term arylthio refers to a S-aryl group.

[0069] As used herein, the term halo is defined as fluoro, chloro, bromo, and iodo. The term haloalkyl refers to an alkyl group that is substituted with at least one halogen, and includes perhalogenated alkyl (i.e., all hydrogen atoms substituted with halogen), for example, CH.sub.3CHCl.sub.2, CH.sub.2ICHBr.sub.2CH.sub.3, or CF.sub.3.

[0070] As used herein, the term oxo refers to a ?O group.

[0071] As used herein, the term amino refers to a NH.sub.2 group, wherein one or both hydrogens can be replaced with an alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group. As used herein, the term amido refers to an amino group that is substituted with a carbonyl moiety (e.g., NRC(?O) or C(?O)NR), wherein R is a substituent on the nitrogen (e.g., alkyl or H). As used herein imine refers to a N(R)?CR.sub.2 group, wherein each R is independently a H, alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group. When referring to a ligand, the term amine refers to a NH.sub.3 group, where one, two, or three hydrogens can be replaced with an alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group. When referring to a ligand, the term amide refers to a NR.sub.2 group, wherein each R is independently a hydrogen, alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group.

[0072] As used herein, the term phosphine refers to a PH.sub.3 group, wherein 0, 1, 2, or 3 hydrogens can be replaced with an alkyl, cycloalkyl, aryl group, heterocycloalkyl, or heteroaryl. As used herein phosphite refers to a P(OR).sub.3 group, wherein each R can individually be an alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group. As used herein, phosphonite refers to a PR(OR).sub.2 group, wherein each R can individually be an alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group. As used herein, phosphinite refers to a PR.sub.2(OR) group, wherein each R can individually be alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group. As used herein, the term diphosphine refers to a P(R.sub.2)(CH.sub.2).sub.nP(R.sub.2) group, wherein each R can individually be an alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group and n can be 1, 2, 3, 4, or 5.

[0073] As used herein, the term carbene refers to a CH.sub.2 ligand, wherein 0, 1, or 2 hydrogens can be replaced with an alkyl, cycloalkyl, aryl, heterocycloalkyl, or heteroaryl group.

[0074] As used herein, the term N-heterocyclic carbene refers to a carbene, wherein the carbene is a ring atom in a heterocycle comprising 1 to 5 nitrogen atoms. Examples of N-heterocyclic carbenes include, but are not limited to,

##STR00006##

wherein, each R group is independently selected from the group of: H, alkyl, cycloalkyl, alkenyl, aryl, alkoxy, aryloxy, heterocycloalkyl, and heteroaryl.

[0075] As used herein, the term metallacycle refers to a cycloalkyl or a heterocycloalkyl wherein one of the ring atoms is replaced by a metal atom.

[0076] As used herein, the term substituted, when used to modify a chemical functional group, refers to the replacement of at least one hydrogen radical on the functional group with a substituent. Substituents can include, but are not limited to, alkyl, cycloalkyl, alkenyl, cycloalkenyl, alkynyl, heterocycloalkyl, heterocycloalkenyl, ether, polyether, thioether, polythioether, aryl, heteroaryl, hydroxyl, oxy, alkoxy, heteroalkoxy, aryloxy, heteroaryloxy, ester, thioester, carboxy, cyano, nitro, amino, amido, acetamide, and halo (e.g., fluoro, chloro, bromo, or iodo). When a chemical functional group includes more than one substituent, the substituents can be bound to the same carbon atom or to two or more different carbon atoms.

[0077] As used herein, bidentate ligand refers to a ligand that has two atoms that can coordinate directly to the metal center of a metal complex, e.g., a single molecule which can form two bonds to a metal center. Non-limiting examples of bidentate ligands include ethylenediamine, bipyridine, phenanthroline, and diphosphine.

[0078] A neutral ligand, as used herein, refers to a ligand that, when provided as a free molecule, does not bear a charge. Examples of neutral ligands include, but are not limited to, water, phosphines, ethers (e.g., tetrahydrofuran), and amines (e.g., pyridine, triethylamine, or the like). An anionic ligand refers to a ligand that, when provided as a free molecule, has a formal charge of ?1. Examples of anionic ligands include, but are not limited to, chloride, methoxy, ethoxy, ispropoxy, tertbutoxy, tertbutyl, neopentyl, triflate, and cyclopentadienyl.

Compounds of the Disclosure

[0079] Provided herein are compounds having a structure represented by formula (I) or dimers thereof:

##STR00007## [0080] wherein the dashed lines are optional double bonds; [0081] M is a transition metal; [0082] L is a neutral or anionic ligand; [0083] each L is independently absent or a neutral or anionic ligand; [0084] Q is selected from S, O, N, NR.sup.5, N(R.sup.5).sub.2, P(R.sup.6).sub.2, C, CR.sup.7, C(R.sup.7).sub.2, BR.sup.8, Si(R.sup.9).sub.2, Se, and Te; [0085] X is selected from a bond, S, O, N, NR.sup.5, Se, Te, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.4-C.sub.10cycloalkyl, Ar.sup.1, C.sub.1-C.sub.4heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; [0086] R.sup.3 is selected from a bond, C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2, and C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2; [0087] each R.sup.1 is independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two geminal R.sup.1 together with the carbon atom to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; [0088] each R.sup.2 is independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or both R.sup.2 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; [0089] each R.sup.6 and R.sup.9 are independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.5, two vicinal R.sup.6, two vicinal R.sup.8, or two vicinal R.sup.9, together with the atoms to which they are attached, form a five- to eight-member cycloalkyl, aryl, heteroaryl, or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; [0090] each R.sup.5, R.sup.7, and R.sup.8 are independently selected from H, C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.7 together with the atoms to which they are attached, form a five- to eight-member cycloalkyl, aryl, heteroaryl, or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; and, [0091] each Ar.sup.1 is independently selected from C.sub.6-C.sub.22 aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S.

[0092] In general, M is a transition metal. In embodiments, M is selected from chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), rhodium (Rh), iridium (Ir), and osmium (Os). In embodiments, M is Mo or W.

[0093] In general, Q is a neutral or anionic ligand. The neutral ligands of the disclosure can be L-type ligands. L-type ligands are known in the art and described in detail throughout, for example, Gray L. Spessard and Gary L. Miessler, Organometallic Chemistry, published by Oxford University Press, 2016, incorporated herein by reference. In embodiments, Q is selected from S, O, N, NR.sup.5, N(R.sup.5).sub.2, P(R.sup.6).sub.2, C, CR.sup.7, C(R.sup.7).sub.2, BR.sup.8, Si(R.sup.9).sub.2, Se, and Te. In embodiments, Q is selected from S, O, N, NR.sup.5, P(R.sup.6).sub.2, C, CR.sup.7, C(R.sup.7).sub.2, and BR.sup.8. In some embodiments, Q is O, N, or NR.sup.5. In embodiments, M is Mo or W and Q is O, N, or NR.sup.5.

[0094] In general, X is selected from a bond, S, O, N, NR.sup.5, Se, Te, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.4-C.sub.10cycloalkyl, Ar.sup.1, C.sub.1-C.sub.4heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, X is selected from, C.sub.1-C.sub.4alkyl, O, NR.sup.5, C.sub.4-C.sub.10cycloalkyl, Ar.sup.1 or C.sub.1-C.sub.8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, X is C.sub.1-C.sub.4alkyl,

##STR00008##

In embodiments, M is Mo or W, Q is O, N, or NR.sup.5, and X is C.sub.1-C.sub.4alkyl,

##STR00009##

[0095] In general, each R.sup.1 is independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two geminal R.sup.1 together with the carbon atom to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, each R.sup.1 is independently selected from H, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20haloalkyl, C.sub.4-C.sub.20cycloalkyl, or Ar.sup.1 or two vicinal R.sup.1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, at least one R.sup.1 is H, C.sub.1-C.sub.5haloalkyl, C.sub.1-C.sub.6alkyl or C.sub.4-C.sub.8cycloalkyl, or Ar.sup.1. In embodiments, each R.sup.1 is H, CH.sub.3, Ph, or CF.sub.3 or two vicinal R.sup.1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S. In embodiments, at least one R.sup.1 is H, CH.sub.3, Ph, or CF.sub.3. In embodiments, each R.sup.1 is H.

[0096] In general, each R.sup.2 is independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or both R.sup.2 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, each R.sup.2 is independently selected from H, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20haloalkyl, C.sub.4-C.sub.20cycloalkyl, or Ar.sup.1. In embodiments, at least one R.sup.2 is H, C.sub.1-C.sub.5haloalkyl, C.sub.1-C.sub.6alkyl or C.sub.4-C.sub.5cycloalkyl, or Ar.sup.1. In embodiments, at least one R.sup.2 is H, CH.sub.3, Ph, or CF.sub.3. In embodiments, each R.sup.2 is H. In embodiments, each R.sup.2 is CH.sub.3. In embodiments, M is Mo or W, Q is O, N, or NR.sup.5, X is C.sub.1-C.sub.4alkyl,

##STR00010##

and each R.sup.2 are H, CH.sub.3, Ph, or CF.sub.3.

[0097] In general, R.sup.3 is selected from a bond, C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2, and C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2. In embodiments, R.sup.3 can be selected from C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2, C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2, or C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2C(R.sup.1).sub.2. In embodiments, R.sup.3 is C(R.sup.1).sub.2 or C(R.sup.1).sub.2C(R.sup.1).sub.2. In embodiments, R.sup.3 is C(R.sup.1).sub.2, and two vicinal R.sup.1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, R.sup.3 is C(R.sup.1).sub.2, and two vicinal R.sup.1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S. In embodiments, M is Mo or W, Q is O, N, or NR.sup.5, X is C.sub.1-C.sub.4alkyl,

##STR00011##

each R.sup.2 are H, CH.sub.3, Ph, or CF.sub.3, R.sup.3 is C(R.sup.1).sub.2 or C(R.sup.1).sub.2C(R.sup.1).sub.2, and each R.sup.1 is H, CH.sub.3, Ph, or CF.sub.3 or two vicinal R.sup.1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S.

[0098] In general, L is a neutral or anionic ligand. The neutral ligands of the disclosure can be L-type ligands. L-type ligands are well known in the art and described in detail throughout, for example, Gray L. Spessard and Gary L. Miessler, Organometallic Chemistry, published by Oxford University Press, 2016, incorporated herein by reference. In embodiments, L comprises one or more functional groups selected from the group of amine, amide, imide, phosphine, phosphite, phosphinite, phosphonite, N-heterocyclic carbene, hydroxyl, oxo, alkoxide, aryloxide, thiol, alkylthiol, arylthiol, carbene, alkyl, cycloalkyl, aryl, heteroaryl, and heterocycloalkyl.

[0099] In embodiments, L is an anionic ligand. In embodiments, L is selected from the group of N(R.sup.5).sub.2, N(R.sup.5), OR.sup.10, SR.sup.11, O, S, OS(O.sub.2)CF.sub.3, carbene, N-heterocyclic carbene, C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R.sup.10 and R.sup.11 are independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, L is selected from the group of N(R.sup.5).sub.2, N(R.sup.5), OR.sup.10, SR.sup.11, OS(O.sub.2)CF.sub.3, carbene, N-heterocyclic carbene, wherein each of R.sup.10 and R.sup.11 are independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, L is selected from the group of N(R.sup.5), OR.sup.10, OS(O.sub.2)CF.sub.3, carbene, and N-heterocyclic carbene, wherein R.sup.10 is selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1 and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, L is selected from the group of N(R.sup.5), OS(O.sub.2)CF.sub.3, and OR.sup.10, wherein R.sup.10 is selected from C.sub.1-C.sub.22 alkyl and Ar.sup.1. In embodiments, L is selected from the group of N(R.sup.5), OS(O.sub.2)CF.sub.3, and OR.sup.10, wherein R.sup.10 is selected from tert-butyl, phenyl, and substituted phenyl and R.sup.5 is selected from Ar.sup.1 and C.sub.4-C.sub.8 cycloalkyl. In embodiments, L is N(R.sup.5) wherein R.sup.5 is selected from Ar.sup.1 and C.sub.4-C.sub.8 cycloalkyl. In embodiments, M is Mo or W, Q is O, N, or NR.sup.5, X is C.sub.1-C.sub.4alkyl,

##STR00012##

[0100] In general, each L is independently absent or a neutral or anionic ligand. In embodiments, at least one L is a neutral ligand. The neutral ligands of the disclosure can be L-type ligands. L-type ligands are well known in the art and described in detail throughout, for example, Gray L. Spessard and Gary L. Miessler, Organometallic Chemistry, published by Oxford University Press, 2016, incorporated herein by reference. In embodiments, each L is independently absent or comprises one or more functional groups selected from the group of amine, amide, imide, phosphine, phosphite, phosphinite, phosphonite, N-heterocyclic carbene, hydroxyl, oxo, alkoxide, aryloxide, thiol, alkylthiol, arylthiol, carbene, alkyl, cycloalkyl, aryl, heteroaryl, and heterocycloalkyl.

[0101] In embodiments, at least one L is an anionic ligand. In embodiments, each L is independently absent or selected from the group of N(R.sup.5).sub.3, N(R.sup.5).sub.2, N(R.sup.5), O(R.sup.10).sub.2, OR.sup.10, S(R.sup.11).sub.2, SR.sup.11, OS(O.sub.2)CF.sub.3, N-heterocyclic carbene, C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.4-C.sub.8heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R.sup.10 and R.sup.11 are independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two R.sup.10 together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand. In embodiments, each L is independently absent or selected from the group of N(R.sup.5).sub.3, N(R.sup.5).sub.2, O(R.sup.10).sub.2, OR.sup.10, S(R.sup.11).sub.2, SR.sup.11, OS(O.sub.2)CF.sub.3, C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.4-C.sub.8heteroaryl, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R.sup.10 and R.sup.11 are independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1, C.sub.4-C.sub.8heteroaryl, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two R.sup.10 together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand.

[0102] In embodiments, at least one L is independently selected from N(R.sup.5).sub.3, N(R.sup.5).sub.2, O(R.sup.10).sub.2, OR.sup.10, N-heterocyclic carbene, or C.sub.1-C.sub.6 alkyl. In embodiments, at least one L is independently selected from Ar.sup.1, C.sub.4-C.sub.8heteroaryl, O(R.sup.10).sub.2, OR.sup.10, or C.sub.1-C.sub.6 alkyl, wherein each of R.sup.10 is independently selected from C.sub.1-C.sub.22 alkyl, Ar.sup.1, or two R.sup.10 together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand. In embodiments, at least one L is independently selected from pyridine, tetrahydrofuran, tert-butyl, or two L together form OCH.sub.2CH.sub.2O. In embodiments, M is Mo or W, Q is O, N, or NR.sup.5, X is C.sub.1-C.sub.4alkyl,

##STR00013##

each R.sup.2 are H, CH.sub.3, Ph, or CF.sub.3, R.sup.3 is C(R.sup.1).sub.2 or C(R.sup.1).sub.2C(R.sup.1).sub.2, each R.sup.1 is H, CH.sub.3, Ph, or CF.sub.3 or two vicinal R.sup.1 together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, L is selected from the group of N(R.sup.5), OS(O.sub.2)CF.sub.3, and OR.sup.10, wherein R.sup.10 is selected from tert-butyl, phenyl, and substituted phenyl and R.sup.5 is selected from Ar.sup.1 and C.sub.4-C.sub.8 cycloalkyl, and L are independently absent or selected from Ar.sup.1, C.sub.4-C.sub.8heteroaryl, O(R.sup.10).sub.2, OR.sup.10, or C.sub.1-C.sub.6 alkyl, wherein each of R.sup.10 is independently selected from C.sub.1-C.sub.22 alkyl, Ar.sup.1, or two R.sup.10 together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand.

[0103] The disclosure further provides compounds selected from the group of:

##STR00014##

[0104] The compounds of the disclosure can be present as a monomer or a dimer. As used herein, the term dimer(s) refers to an oligomer consisting of two monomers joined by bonds that can be either strong or weak, covalent or intermolecular. The compounds of the disclosure can comprise homodimers, i.e. the dimer comprises two identical monomers. The compounds of the disclosure can comprise cyclic dimers, i.e. the dimer comprises two monomers connected through two or more sites on each monomer. Generally, the compounds of the disclosure can form dimers in solution; however, the compounds of the disclosure can also be present as monomers.

[0105] In various embodiments, the compound is a dimer. In some embodiments, the compound is a dimer having a structure represented by formula (I-dimer):

##STR00015##

[0106] In various embodiments, the compound is a dimer with the structure:

##STR00016##

Synthesizing Compounds of Formula (I)

[0107] The disclosure further provides methods of making the compound having a structure represented by formula (I), the method includes admixing a compound of formula (II) and a compound of formula (III) to form a compound of formula (IV) or dimer thereof, and admixing a compound of formula (IV), or dimer thereof with a deprotonating agent to form the compound of formula (I), or dimer thereof:

##STR00017## [0108] wherein the dashed lines are optional double bonds; [0109] M is a transition metal; [0110] L.sup.a and L.sup.b are neutral or anionic ligands; [0111] each L.sup.a is independently absent or a neutral or anionic ligand; [0112] each L.sup.b is independently absent or a neutral or anionic ligand; [0113] Q.sup.a and Q.sup.b are selected from S, O, N, NR.sup.5a, N(R.sup.5a).sub.2, P(R.sup.6a).sub.2, C, CR.sup.7a, C(R.sup.7a).sub.2, BR.sup.8a, Si(R.sup.9a).sub.2, Se, and Te; [0114] Z is selected from H, halo, or a counterion for Q.sup.a; [0115] X.sup.a and X.sup.b are selected from S, O, N, NR.sup.5a, Se, Te, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.4-C.sub.10cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.4heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; [0116] R.sup.3a and R.sup.3b are selected from a bond, C(R.sup.1a).sub.2, C(R.sup.1a).sub.2C(R.sup.1a).sub.2, C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2, C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2, and C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2; [0117] each R.sup.1a and R.sup.1b are independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, two geminal R.sup.1a together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.1a together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; [0118] each R.sup.2a and R.sup.2b is independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or both R.sup.2a together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; [0119] each R.sup.5a, R.sup.6a, R.sup.7a, R.sup.8a and R.sup.9a is independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.5a, two vicinal R.sup.6a, two vicinal R.sup.7a, two vicinal R.sup.8a, or two vicinal R.sup.9a, together with the atoms to which they are attached, form a five- to eight-member cycloalkyl, aryl, heteroaryl, or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; [0120] each Ar.sup.1a is independently selected from C.sub.6-C.sub.22 aryl and a 5-12 membered heteroaryl comprising from 1 to 3 ring heteroatoms selected from O, N, and S.

[0121] In general, L.sup.a and L.sup.b can be any ligand as defined herein for L. L.sup.a and L.sup.b can comprise one or more functional groups selected from the group of amine, amide, imide, phosphine, phosphite, phosphinite, phosphonite, N-heterocyclic carbene, hydroxyl, oxo, alkoxide, aryloxide, thiol, alkylthiol, arylthiol, carbene, alkyl, cycloalkyl, aryl, heteroaryl, and heterocycloalkyl. L.sup.a and L.sup.b can be L-type ligands. L-type ligands are well known in the art and described in detail throughout, for example, Gray L. Spessard and Gary L. Miessler, Organometallic Chemistry, published by Oxford University Press, 2016, incorporated herein by reference. In embodiments, L.sup.a and L.sup.b are the same.

[0122] In embodiments, L.sup.a and/or L.sup.b is an anionic ligand. In embodiments, L.sup.a and/or L.sup.b is selected from the group of N(R.sup.5a).sub.2, N(R.sup.5a), OR.sup.10a, SR.sup.11a, O, S, OS(O.sub.2)CF.sub.3, carbene, N-heterocyclic carbene, C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R.sup.10a and R.sup.11a are independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, L.sup.a and/or L.sup.b is selected from the group of N(R.sup.5a).sub.2, N(R.sup.5a), OR.sup.10a, SR.sup.11a, OS(O.sub.2)CF.sub.3, carbene, N-heterocyclic carbene, wherein each of R.sup.10 and R.sup.11 are independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, L.sup.a and/or L.sup.b is selected from the group of N(R.sup.5a), OR.sup.10a, OS(O.sub.2)CF.sub.3, carbene, and N-heterocyclic carbene, wherein R.sup.10a is selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1a and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, L.sup.a and/or L.sup.b is selected from the group of N(R.sup.5a), OS(O.sub.2)CF.sub.3, and OR.sup.10a, wherein R.sup.10a is selected from C.sub.1-C.sub.22 alkyl and Ar.sup.1a. In embodiments, L.sup.a and/or L.sup.b is selected from the group of N(R.sup.5a), OS(O.sub.2)CF.sub.3, and OR.sup.10a, wherein R.sup.10a is selected from tert-butyl, phenyl, and substituted phenyl and R.sup.5 is selected from Ar.sup.1a and C.sub.4-C.sub.8 cycloalkyl. In embodiments, L.sup.a and/or L.sup.b is N(R.sup.5a) wherein R.sup.5a is selected from Ar.sup.1a and C.sub.4-C.sub.8 cycloalkyl. Ar.sup.1a can be any Ar.sup.1 as defined herein. R.sup.5a can be any R.sup.5 as defined herein.

[0123] In general, L.sup.a and L.sup.b can be any ligand as defined herein for L. When present, L.sup.a and L.sup.b can be neutral ligands or an anionic ligands. The neutral ligands of the disclosure can be L-type ligands. L-type ligands are well known in the art and are described in detail throughout, for example, Gray L. Spessard and Gary L. Miessler, Organometallic Chemistry, published by Oxford University Press, 2016, incorporated herein by reference. In embodiments, each L.sup.a and L.sup.b is independently absent or comprises one or more functional groups selected from the group of amine, amide, imide, phosphine, phosphite, phosphinite, phosphonite, N-heterocyclic carbene, hydroxyl, oxo, alkoxide, aryloxide, thiol, alkylthiol, arylthiol, carbene, alkyl, cycloalkyl, aryl, heteroaryl, and heterocycloalkyl.

[0124] In embodiments, at least one L.sup.a and L.sup.b is an anionic ligand and at least one L.sup.a and L.sup.b is a neutral ligand. In embodiments, each L.sup.a and/or L.sup.b is independently absent or selected from the group of N(R.sup.5a).sub.3, N(R.sup.5a).sub.2, N(R.sup.5a), O(R.sup.10a).sub.2, OR.sup.10a, S(R.sup.11a).sub.2, SR.sup.11a, OS(O.sub.2)CF.sub.3, N-heterocyclic carbene, C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R.sup.10a and R.sup.11a are independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two R.sup.10 together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand. In embodiments, each L.sup.a and/or L.sup.b is independently absent or selected from the group of N(R.sup.5a).sub.3, N(R.sup.5a).sub.2, O(R.sup.10a).sub.2, OR.sup.10a, S(R.sup.11a).sub.2, SR.sup.11a, OS(O.sub.2)CF.sub.3, C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1a, C.sub.4-C.sub.8heteroaryl, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, wherein each of R.sup.10a and R.sup.11a are independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1a, C.sub.4-C.sub.8heteroaryl, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two R.sup.10a together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand.

[0125] In embodiments, at least one L.sup.a and L.sup.b is independently selected from N(R.sup.5a).sub.3, N(R.sup.5a).sub.2, O(R.sup.10a).sub.2, OR.sup.10a, N-heterocyclic carbene, or C.sub.1-C.sub.6 alkyl. In embodiments, at least one L.sup.a and/or L.sup.b is independently selected from Ar.sup.1a, C.sub.4-C.sub.8heteroaryl, O(R.sup.10a).sub.2, OR.sup.10a, or C.sub.1-C.sub.6 alkyl, wherein each of R.sup.10 is independently selected from C.sub.1-C.sub.22 alkyl, Ar.sup.1a, or two R.sup.10a together with the oxygen atom(s) to which they are attached form a four- to eight-member ring or bidentate ligand. In embodiments, at least one L.sup.a and/or L.sup.b is independently selected from pyridine, tetrahydrofuran, tert-butyl, or two L.sup.a and/or L.sup.b together form OCH.sub.2CH.sub.2O. In embodiments, each L.sup.b corresponds to (e.g., is the same as) an L.sup.a.

[0126] In general, Q.sup.a and Q.sup.b can be any ligand as defined herein for Q. Q.sup.a and Q.sup.b can be neutral or anionic ligands. The neutral ligands of the disclosure can be L-type ligands as disclosed herein. Generally, Q.sup.a and Q.sup.b are selected from S, O, N, NR.sup.5a, N(R.sup.5a).sub.2, P(R.sup.6a).sub.2, C, CR.sup.7a, C(R.sup.7a).sub.2, BR.sup.8a, Si(R.sup.9a).sub.2, Se, and Te. In embodiments, Q.sup.a and Q.sup.b are selected from S, O, N, NR.sup.5a, P(R.sup.6a).sub.2, C, CR.sup.7a, C(R.sup.7a).sub.2, and BR.sup.8a. In embodiments, Q.sup.a and Q.sup.b are selected from O, N, or NR.sup.5a. In embodiments, Q.sup.a and Q.sup.b are the same. R.sup.6a, R.sup.7a, R.sup.8a, and R.sup.9a can be any R.sup.6, R.sup.7, R.sup.8, or R.sup.9 as defined herein, respectively.

[0127] In general, X.sup.a and X.sup.b are selected from a bond, S, O, N, NR.sup.5a, Se, Te, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkyl, C.sub.2-C.sub.4alkenyl, C.sub.4-C.sub.10cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.4heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, X.sup.a and X.sup.b are selected from C.sub.1-C.sub.4alkyl, O, NR.sup.5a, C.sub.4-C.sub.10cycloalkyl, Ar.sup.1a, or C.sub.1-C.sub.8heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, X.sup.a and X.sup.b are C.sub.1-C.sub.4alkyl,

##STR00018##

[0128] In general, Z is selected from H, halo, or a counterion for Q.sup.a. In embodiments, Z is H or a counterion for Q.sup.a. In embodiments, Z is Li, Na, or K.

[0129] In general, each R.sup.1a and R.sup.1b can be any R.sup.1 as defined herein. R.sup.1a and R.sup.1b can be independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two geminal R.sup.1a or R.sup.1b together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.1a or R.sup.1b together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S.

[0130] In embodiments, each R.sup.1a and R.sup.1b is independently selected from H, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20haloalkyl, C.sub.4-C.sub.20cycloalkyl, or Ar.sup.1a or two vicinal R.sup.1a or R.sup.1b together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, at least one R.sup.1a and/or R.sup.1b is H, C.sub.1-C.sub.5haloalkyl, C.sub.1-C.sub.6alkyl or C.sub.4-C.sub.8cycloalkyl, or Ar.sup.1a. In embodiments, at least one R.sup.1a and/or R.sup.1b is H, C.sub.1-C.sub.5haloalkyl, C.sub.1-C.sub.6alkyl or C.sub.4-C.sub.8cycloalkyl, or Ar.sup.1a. In embodiments, each R.sup.1a and/or R.sup.1b is H, CH.sub.3, Ph, or CF.sub.3 or two vicinal R.sup.1a or R.sup.1b together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S. In embodiments, at least one R.sup.1a and/or R.sup.1b is H, CH.sub.3, Ph, or CF.sub.3. In embodiments, each R.sup.1a and/or R.sup.1b is H. In embodiments, each R.sup.1b corresponds to (e.g., is the same as) an R.sup.1a.

[0131] In general, each R.sup.2a and R.sup.2b can be any R.sup.2 as defined herein. R.sup.2a and R.sup.2b can be independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or both R.sup.2a together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S.

[0132] In embodiments, each R.sup.2a and/or R.sup.2b is independently selected from H, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20haloalkyl, C.sub.4-C.sub.20cycloalkyl, or Ar.sup.1a. In embodiments, at least one R.sup.2a and/or R.sup.2b is H, C.sub.1-C.sub.5haloalkyl, C.sub.1-C.sub.6alkyl or C.sub.4-C.sub.8cycloalkyl, or Ar.sup.1a. In embodiments, at least one R.sup.2a and/or R.sup.2b is H, CH.sub.3, Ph, or CF.sub.3. In embodiments, each R.sup.2a and/or R.sup.2b is H. In embodiments, each R.sup.2a and/or R.sup.2b is CH.sub.3. In embodiments, each R.sup.2b corresponds to (e.g., is the same as) an R.sup.2a.

[0133] In general, R.sup.3a and R.sup.3b can be any R.sup.3 as defined herein. R.sup.3a and/or R.sup.3b can be selected from a bond, C(R.sup.1a).sub.2, C(R.sup.1a).sub.2C(R.sup.1a).sub.2, C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2, C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2, and C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2. In embodiments, R.sup.3a and/or R.sup.3b is C(R.sup.1a).sub.2, C(R.sup.1a).sub.2C(R.sup.1a).sub.2, C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2, or C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2C(R.sup.1a).sub.2. In embodiments, R.sup.3a and/or R.sup.3b is C(R.sup.1a).sub.2 or C(R.sup.1a).sub.2C(R.sup.1a).sub.2. In embodiments, R.sup.3a and/or R.sup.3b is C(R.sup.1a).sub.2, and two vicinal R.sup.1a together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S, or a five- to eight-member cycloalkyl or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, R.sup.3a and/or R.sup.3b is C(R.sup.1).sub.2, and two vicinal R.sup.1a together with the carbon atoms to which they are attached, form a six-member aryl or heteroaryl comprising 1 to 4 heteroatoms selected from O, N, and S. In embodiments, each R.sup.3b corresponds to (e.g., is the same as) an R.sup.3a.

[0134] In general, each R.sup.5a, R.sup.6a, R.sup.7a, R.sup.8a, and R.sup.9a can be any R.sup.5, R.sup.6, R.sup.7, R.sup.8, and R.sup.9 disclosed herein, respectively. In embodiments, each R.sup.5a, R.sup.6a, R.sup.7a, R.sup.8a, and R.sup.9a is independently selected from C.sub.1-C.sub.22 alkyl, C.sub.4-C.sub.8 cycloalkyl, Ar.sup.1a, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.5a, two vicinal R.sup.6a, two vicinal R.sup.7a, two vicinal R.sup.8a, or two vicinal R.sup.9a, together with the atoms to which they are attached, form a five- to eight-member cycloalkyl, aryl, heteroaryl, or heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S.

[0135] In general, M is a transition metal. In embodiments, M is selected from chromium (Cr), molybdenum (Mo), tungsten (W), iron (Fe), ruthenium (Ru), rhodium (Rh), iridium (Ir), and osmium (Os). In embodiments, M is Mo or W.

[0136] In general, the deprotonating agent comprises an ylide, LiN(SiMe.sub.3).sub.2, or KH. In embodiments, the deprotonating agent is Ph.sub.3P?CH.sub.2.

[0137] In general, the compound of formula (II) and the compound of formula (III) can be admixed under conditions sufficient to form a compound having a structure represented by formula (I) or dimer thereof. In embodiments, the admixing comprises a molar ratio of the compound of formula (II) and the compound of formula (III) of at least about 1:0.8, respectively. In embodiments, the admixing compromises the compound of formula (II) and the compound of formula (III) in a molar ratio of at least 1:0.8, or in a range of about 1:0.8 to about 1:1.5. In general, increasing the concentration of the compound of formula (II) can increase the rate the reaction to form the compound of formula (I) or dimer thereof; however, as the concentration of the compound of formula (III) increases, the likelihood of intermolecular reactions also increases, such as, the aggregation of multiple metal complexes, or over ligation of the metal center with the compound of formula (III).

[0138] In general, about one molar equivalent (e.g., at least 0.8 molar equivalents) of the compound of formula (III) per molar equivalent of the compound of formula (II) can be used to form the compound of formula (I) or dimer thereof.

[0139] In general, the compound of formula (IV) or dimer thereof and the deprotonating agent can be admixed under conditions sufficient to form the compound having a structure represented by formula (I), or dimer thereof. In embodiments, the admixing comprises a molar ratio of the compound of formula (IV) and the deprotonating agent of at least about 1:1, respectively. It will be understood that the molar ratio for admixing a compound of formula (IV) with the deprotonating agent refers to the molar ratio of the total monomers of formula (IV) (whether present as individual compounds or joined as a dimer) to the deprotonating agent. In embodiments, the admixing comprises the compound of formula (IV) and the deprotonating agent in a molar ratio of at least 1:1, or in a range of about 1:1 to about 1:10, or about 1:1 to about 1:5, or about 1:1 to about 1:3. In general, increasing the concentration of deprotonating agent can increase the rate the reaction to form the compound of formula (I); however, as the concentration of the deprotonating agent increases, the likelihood of intermolecular reactions also increases, such as, the aggregation of multiple metal complexes, or over ligation of the metal center with the deprotonating agent.

[0140] In general, about one molar equivalent (e.g., at least 1 molar equivalent) of the deprotonating agent per molar equivalent of the compound of formula (IV) can be used to form the compound of formula (I) or dimer thereof.

[0141] In embodiments, the admixing of the compound of formula (II) and the compound of formula (III) or the compound of formula (IV) and the deprotonating agent can occur neat, for example, in cases where the compound of formula (II) or the compound of formula (III) or the compound of formula (IV) is a liquid. In embodiments, the admixing of the compound of formula (II) and the compound of formula (III) or the compound of formula (IV) and the deprotonating agent can occur in solution. Suitable solvents include but are not limited to, nonpolar aprotic solvents, such as, benzene, toluene, hexanes, pentanes, trichloromethane, chloro-substituted benzenes, deuterated analogs thereof, or combinations thereof.

[0142] In embodiments, the admixing of the compound of formula (II) and the compound of formula (III) comprises a solvent. In refinements of the foregoing embodiments, the solvent comprises a nonpolar aprotic solvent. In further refinements of the foregoing embodiments, the nonpolar aprotic solvent comprises benzene, toluene, hexanes, pentanes, trichloromethane, chloro-substituted benzenes, deuterated analogs thereof, or combinations thereof. In embodiments, the admixing of the compound of formula (IV) and the deprotonating agent comprises a solvent. In refinements of the foregoing embodiments, the solvent comprises a nonpolar aprotic solvent. In further refinements of the foregoing embodiments, the nonpolar aprotic solvent comprises benzene, toluene, hexanes, pentanes, trichloromethane, chloro-substituted benzenes, deuterated analogs thereof, or combinations thereof.

[0143] The admixing of the compound of formula (II) and the compound of formula (III), and the compound of formula (IV) and the deprotonating agent can occur at any suitable temperature for any suitable time. It is well understood in the art that the rate of a reaction during admixing can be controlled by tuning the temperature. Thus, in general, as the reaction temperature increases the reaction time can decrease.

[0144] Reaction temperatures can be in a range of about ?80? C. to about 100? C., about ?70? C. to about 80? C., about ?50? C. to about 75? C., about ?25? C. to about 50? C., about 0? C. to about 35? C., about 5? C. to about 30? C., about 10? C. to about 30? C., about 15? C. to about 25? C., about 20? C. to about 30? C., or about 20? C. to about 25? C., for example, about 0? C., about 5? C., about 10? C., about 15? C., about 20? C., about 25? C., about 30? C., or about 35? C. In embodiments, the admixing of the compound of formula (II) and the compound of formula (III) occurs at a temperature in a range of about 0? C. to about 35? C., or about 10? C. to about 30? C., or about 20? C. to about 30? C. In embodiments, the admixing of the compound of formula (IV) and the deprotonating agent occurs at a temperature in a range of about 0? C. to about 35? C., or about 10? C. to about 30? C., or about 20? C. to about 30? C.

[0145] Reaction times can be instantaneous or in a range of about 30 seconds to about 72 hours, about 1 minute to about 72 hours, about 5 minutes to about 72 hours, about 10 minutes to about 48 hours, about 15 minutes to about 24 hours, about 1 minute to about 24 hours, about 5 minutes to about 12 hours, about 10 minutes to about 6 hours, about 20 minutes to about 1 hour, about 20 minutes (min) to about 12 hours (h), about 25 min to about 6 h, or about 30 min to about 3 h, for example, about 30 seconds, 1 min, 5 min, 10 min, 15 min, 20 min, 25 min, 30 min, 35 min, 40 min, 45 min, 50 min, 55 min, 60 min, 75 min, 90 min, 105 min, 2 h, 3 h, 4 h, 5 h, 6 h, 12 h, 18 h, 24 h, 36 h, 48 h, 60 h, or 72 h. When the reaction temperature increases above 100? C., generally the risk of decomposition of the product increases. In embodiments, the admixing of the compound of formula (II) and the compound of formula (III) occurs for a time in a range of about 1 minute to about 24 hours, or about 5 minutes to about 12 hours, or about 10 minutes to about 6 hours, or about 20minutes to about 1 hour. In embodiments, the admixing of the compound of formula (IV) and the deprotonating agent occurs for a time in a range of about 1 minute to about 24 hours, or about 5 minutes to about 12 hours, or about 10 minutes to about 6 hours, or about 20minutes to about 1 hour.

[0146] As demonstrated in the examples below, the compounds of formula (I) are dynamic in solution and generally have a dimer structure in the solid state.

Methods of Using Compounds of Formula (I)

[0147] The disclosure further provides a method of preparing a cyclic polymer, the method including admixing a plurality of alkene monomers, alkyne monomers, or both in the presence of the compound of formula (I) or dimer thereof, under conditions sufficient to polymerize the plurality of alkene monomers, alkyne monomers, or both to form the cyclic polymer.

[0148] Advantageously, compounds having a structure represented by formula (I), or dimers thereof, can generate high-molecular weight cyclic polymers.

[0149] Cyclic polymers can be prepared from any monomer that includes a carbon-carbon double bond or a carbon-carbon triple bond. In embodiments, the admixing comprises a plurality of alkyne monomers. In embodiments, the admixing comprises a plurality of alkene monomers.

[0150] Suitable alkyne monomers include, but are not limited to, C.sub.2-C.sub.20alkynes, C.sub.8-C.sub.20 monocyclic cycloalkynes, 8-20 membered monocyclic heterocycloalkynes comprising one to five ring heteroatoms selected from S, O, and N, C.sub.8-C.sub.20polycyclic cycloalkynes, or 8-20 membered polycyclic heterocycloalkynes comprising one or more ring heteroatoms selected from S, O, and N. The alkyne monomers can be substituted or unsubstituted. For example, the plurality of alkyne monomers can include cyclooctyne, cycloocta-1,5-diyne, phenylacetylene or

##STR00019##

[0151] Suitable alkene monomers include, but are not limited to, C.sub.3-C.sub.20alkenes, C.sub.5-C.sub.20 monocyclic cycloalkenes, 5-20 membered monocyclic heterocycloalkenes comprising one to five ring heteroatoms selected from S, O, and N, C.sub.5-C.sub.20polycyclic cycloalkenes, or 5-20 membered polycyclic heterocycloalkenes comprising one or more ring heteroatoms selected from S, O, and N. The alkene monomers can be substituted or unsubstituted. For example, the plurality of alkene monomers can include norbornene or cyclooctene.

[0152] The polymerization reaction occurs upon combining in a fluid state the compound having a structure according to formula (I), or dimer thereof, and the plurality of alkenes, alkynes, or both. In some embodiments the reaction can be in neat alkene, alkyne, or both, wherein the monomers are provided in a fluid state. In some embodiments, the reaction can include a solvent such that the fluid state can be in solution.

[0153] Examples of solvents that may be used in the polymerization reaction include, but are not limited to, organic (e.g., nonpolar aprotic solvents) that are inert under the polymerization conditions, such as aromatic hydrocarbons, halogenated hydrocarbons, ethers, aliphatic hydrocarbons, or mixtures thereof. In embodiments, the solvent is a nonpolar aprotic solvent. In embodiments, the nonpolar aprotic solvent comprises benzene, toluene, deuterated analogs thereof, or combinations thereof.

[0154] The polymerization can be carried out at, for example, ambient temperatures (e.g., about 20? C. to about 25? C.) at dry conditions (e.g., about 0-1% RH) under an inert atmosphere (e.g., nitrogen or argon). Polymerization temperatures can be in a range of about 0? C. to about 35? C., about 10? C. to about 30? C., or about 20? C. to about 30? C. Reaction times can be instantaneous or otherwise until completion. The progress of the reaction can be monitored by standard techniques, e.g., nuclear magnetic resonance (NMR) spectroscopy. In embodiments, the reaction times are in a range of about 30 minutes to about 12 hours, about 1 hour to about 3 hours, about 1 hour to about 10 hours, about 1 hour to about 24 hours, or about 5 hours to about 24 hours. Polymerization times will vary, depending on the particular monomer and the metal complex. The rate of the reaction can decrease if the temperature of the polymerization is below room temperature. Reactions that occur over 100? C. can lead to the catalyst decomposing.

[0155] The method of preparing cyclic polymers includes the plurality of alkene monomers, alkyne monomers, or both, and the compound of formula (I), or dimer thereof, in a molar ratio in a range of about 1,000,000:1 to about 10:1, or about 100,000:1 to about 50:1, or about 50,000:1 to about 100:1, or about 50,000:1 to about 500:1, or about 50,000:1 to about 100:1, respectively. For example, the molar ratio of the plurality of alkene monomers, alkyne monomers, or both, to the compound of formula (I), or dimer thereof, is about 1,000,000:1, about 500,000:1, about 100,000:1, about 50,000:1, about 25,000:1, about 10,000:1, about 5,000:1, about 1000:1, about 500:1, or about 100:1.

[0156] Polymerization may be terminated at any time by addition of a solvent effective to precipitate the polymer, for example, methanol. The precipitated polymer may then be isolated by filtration or other conventional means.

[0157] The molecular weight of the cyclic polymers can be small, equivalent to oligomers of three to ten repeating units, or the molecular weights can be of any size up to tens and hundreds of thousands or millions in molecular weight, for example, in a range of about 200 Da to about 5,000,000 Da, about 500 Da to about 4,000,000 Da, about 1,000 Da to about 3,000,000 Da, about 5,000 Da to about 2,000,000 Da or about 10,000 Da to about 1,000,000 Da. The molecular weight is measured using gel permeation chromatography (GPC) and is calculated in number averaged molecular weight.

[0158] The disclosure further provides cyclic polymers, synthesized via the method above including admixing a plurality of alkene monomers, alkyne monomers, or both in the presence of the compound of formula (I), or dimer thereof, under conditions sufficient to polymerize the plurality of alkene monomers, alkyne monomers, or both to form the cyclic polymer, having a structure represented by formula (V) or formula (VI):

##STR00020## [0159] wherein the dashed line is an optional double or triple bond; [0160] each R.sup.12 is independently absent, H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C.sub.1-C.sub.20alkoxy, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.12 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl, heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, aryl, or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S; [0161] each R.sup.13 is independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C.sub.1-C.sub.20alkoxy, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S; [0162] and n is an integer of at least 2.

[0163] In general, the dashed line is optionally a double bond or a triple bond. In embodiments, the dashed line can be a double bond. In embodiments, the dashed line can be a triple bond.

[0164] In general, each R.sup.12 is independently absent, H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C.sub.1-C.sub.20alkoxy, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.12 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl, heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, aryl, or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S. In embodiments, each R.sup.12 is independently absent, H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.1-C.sub.20alkoxy, or C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.12 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl, heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, aryl, or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S. In embodiments, each R.sup.12 is independently absent, H, C.sub.1-C.sub.4haloalkyl, C.sub.1-C.sub.4alkyl, C.sub.1-C.sub.4alkoxy, or C.sub.1-C.sub.4heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.12 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl, heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, aryl, or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S. In embodiments, each R.sup.12 is independently absent, H, C.sub.1-C.sub.4alkyl, or C.sub.1-C.sub.4heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, or two vicinal R.sup.12 together with the carbon atoms to which they are attached, form a five- to eight-member cycloalkyl, heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, aryl, or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S. In embodiments, each R.sup.12 is independently absent, H, CH.sub.3, or tert-butyl, or two vicinal R.sup.12 together with the carbon atoms to which they are attached, form a five- to eight-member aryl or heteroaryl comprising 1 to 5 heteroatoms selected from O,N, and S. In embodiments, each R.sup.12 is independently absent or H. In embodiments, each R.sup.12 is independently absent or H, or two vicinal R.sup.12 together with the carbon atoms to which they are attached, form a five- to eight-member aryl.

[0165] In general, each R.sup.13 is independently selected from H, C.sub.1-C.sub.20haloalkyl, C.sub.1-C.sub.20alkyl, C.sub.2-C.sub.20alkenyl, C.sub.4-C.sub.20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C.sub.1-C.sub.20alkoxy, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, each R.sup.13 is independently selected from, H, C.sub.1-C.sub.20alkyl, C.sub.4-C.sub.20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C.sub.1-C.sub.20alkoxy, C.sub.1-C.sub.20heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.1-C.sub.20heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S. In embodiments, each R.sup.13 is independently selected from, H, C.sub.1-C.sub.15alkyl, C.sub.4-C.sub.20cycloalkyl, aryl, heteroaryl comprising 1 to 5 heteroatoms selected from O, N, and S, C.sub.1-C.sub.15alkoxy, C.sub.1-C.sub.15heteroalkyl comprising 1 to 5 heteroatoms selected from O, N, and S, and C.sub.4-C.sub.15heterocycloalkyl comprising 1 to 5 heteroatoms selected from O, N, and S.

[0166] In general, n is an integer of at least 2. In embodiments, n can be in a range of about 2 to about 5,000,000, about 2 to about 1,000,000, about 2 to about 500,000, about 2 to about 100,000, about 2 to about 50,000, about 5 to about 100,000, about 10 to about 500,000, about 25 to about 250,000, or about 50 to about 50,000.

[0167] In embodiments, the cyclic polymer is a compound having the structure:

##STR00021## [0168] wherein n is an integer of at least 2. This structure may also be represented as the structure:

##STR00022##

EXAMPLES

Materials and Methods

[0169] Benzene, hexanes, diethyl ether, tetrahydrofuran, pentane, and toluene were degassed, dried using a GlassContour drying column or equivalent, and stored over 3 ? molecular sieves prior to use. 1,2-benzenedimethanol was purchased from Oakwood Chemical and recrystallized from diethyl ether. W(C.sup.tBu)(CH.sub.2.sup.tBu)(O-2,6-.sup.iPr.sub.2C.sub.6H.sub.3) was prepared according to the method published in Tonzetich et. al, Organometallics 2007, 26, 475-477. All other chemicals were used without purification unless otherwise noted.

[0170] The overall scheme for the ligand synthesis is shown in FIG. 1.

Example 1Synthesis of 2-(bromomethyl)benzenemethanol

[0171] A 2-neck round bottom flask equipped with a stir bar, septum and stopcock flow adapter under argon was charged with 1,2-benzenedimethanol (7.654 g, 55.402 mmol) and 400 mL of dry dichloromethane. The mixture was stirred and cooled in an ice/water bath, 0? C. Through the septum, phosphorus tribromide (1.75 mL, 18.6 mmol) was added dropwise via syringe to the cold stirring solution. The reaction was stirred at 0? C. for 2 h then warmed naturally to ambient temperature while stirring for 1.5 h. The solution was filtered through silica and the volatiles were removed in vacuo. The products were separated via column chromatography (SiO.sub.2; hexanes/ethyl acetate 17:1). Upon solvent removal in vacuo 2-(bromomethyl)benzenemethanol was obtained.

[0172] .sup.1H NMR (300 MHz, C.sub.6D.sub.6): ? 7.15 (s, 1H, ArH), 6.99 (td, 1H, J=7.2, 1.9 Hz, ArH), 6.96-6.90 (m, 2H, ArH), 4.41 (d, 2H, J=5.7 Hz, HOCH.sub.2.sup.7), 4.17 (s, 2H, BrCH.sub.2.sup.8), 0.87 (d, 1H, J=5.8 Hz, OH).

[0173] .sup.13C NMR (101 MHz, C.sub.6D.sub.6): ? 140.0, 135.8, 130.7, 129.0, 128.6, 62.3, 31.0.

Example 2Synthesis of (3-(trimethylsilyl)prop-2-yn-1-yl)magnesium bromide

[0174] A dry round bottom flask equipped with a stir bar was charged with zinc bromide (0.059 g, 0.26 mmol), magnesium turnings (0.642 g. 26.4 mmol), dry diethyl ether (10 mL) and fitted with a dropping funnel containing a solution of 3-bromo-1-(trimethylsilyl)-1-propyne (2.511 g, 13.13 mmol) in diethyl ether (8 mL). The apparatus was attached to a Schlenk line under argon and the addition started at ambient temperature. Once an exothermic reaction was observed, the flask was chilled to 0? C. in an ice/water bath. Upon completion of the addition the reaction was stirred for 2 h at 0? C. The concentration was found to be 0.53 M via titration of a water quenched aliquot of the reaction mixture with 0.10 M HCl(aq) with bromomethyl blue as an indicator. The reaction mixture allowed to settle and the solution was cannula transferred into the next reaction step.

Example 3Synthesis of (2-(4-(trimethylsilyl)but-3-yn-1-yl)phenyl)methanol

[0175] A Schlenk flask equipped with a stir bar was charged with 2-(bromomethyl)-benzenemethanol (0.862 g, 4.28 mmol) as prepared in Example 1, and 30 mL of dry diethyl ether. To the flask was attached an addition funnel and the apparatus was placed on a Schlenk line. The flask was chilled, stirring, in an ice/water bath, 0? C. The solution of the generated Grignard, (3-(trimethylsilyl)prop-2-yn-1-yl)magnesium bromide prepared in Example 2 was transferred to the addition funnel via cannula (approx. 18 mL, 0.72 M). The Grignard solution was added dropwise to the chilled flask with stirring. After the complete addition, the reaction flask was allowed to warm naturally to ambient temperature and stirred overnight (12 hours). Cool deionized (DI) water was added to quench the reaction, and additional ether was added to dilute the organic layer. The organic layer was washed with DI water, brine, and dried over magnesium sulfate. The ether was filtered and the solvent removed in vacuo. The products were separated via column chromatography (SiO.sub.2; hexanes/ethyl acetate 4:1).

[0176] .sup.1H NMR (300 MHz, C.sub.6D.sub.6): ? 7.20-7.17 (m, 1H, ArH), 7.09-7.04 (m, 2H, ArH), 7.02-6.99 (m, 1H, ArH), 4.32 (s, 2H, OHCH.sub.2.sup.7), 2.71 (t, 2H, J=7.4 Hz, CH.sub.2.sup.8), 2.36 (t, 2H, J=7.4 Hz, CH.sub.2.sup.9), 1.08 (s, 1H, OH), 0.18 (s, 9H, TMS).

[0177] .sup.13C NMR (101 MHz, C.sub.6D.sub.6): ? 139.3, 139.0, 129.9, 128.8, 127.9, 126.8, 107.4, 85.6, 63.1, 31.5, 22.1, 0.2.

Example 4Synthesis of (2-(but-3-yn-1-yl)phenyl)methanol

[0178] In a round bottom flask equipped with a stir bar, 14 mL diethyl ether and (2-(4-(trimethylsilyl)but-3-yn-1-yl)phenyl)methanol (0.213 g, 0.916 mmol) as prepared in Example 3 were added. The solution was stirred and a 1.16 M solution of TBAF in THF (0.95 mL, 1.1 mmol) was added. The mixture quickly turned opaque with a yellow oil on the bottom of the flask and was left stirring overnight (12 hours). The mixture was diluted with ether, and then washed with 1.0 M HCl (20 mL) followed by deionized water and brine. The organic layer was dried over magnesium sulfate, filtered, and then solvents removed in vacuo.

[0179] .sup.1H NMR (600 MHz, C.sub.6D.sub.6): ? 7.19 (dd, J=6.9, 2.4 Hz, 1H, ArH), 7.09-7.02 (m, 2H, ArH), 6.97 (dd, J=7.0, 2.1 Hz, 1H, ArH), 4.29 (s, 2H, CH.sub.2.sup.7), 2.67 (t, J=7.6 Hz, 2H, CH.sub.2.sup.8), 2.25 (td, J=7.6, 2.6 Hz, 2H, CH.sub.2.sup.9), 1.75 (t, J=2.7 Hz, 1H, CH.sup.11), 1.13 (s, 1H, OH).

[0180] .sup.13C NMR (101 MHz, C.sub.6D.sub.6): ? 139.2, 138.8, 129.6, 128.6, 128.0, 126.8, 84.0, 69.6, 63.0, 31.4, 20.4.

Example 5Synthesis of (2-(4-phenylbut-3-yn-1-yl)phenyl)methanol

[0181] A round bottom flask equipped with a stir bar was charged with iodobenzene (1.132 g, 5.548 mmol), tetrakistriphenylphosphine palladium(0) (0.0644 g, 0.0557 mmol), copper (I) iodide (0.0211 g, 0.111 mmol), and triethylamine. The mixture was stirred under argon and the (2-(but-3-yn-1-yl)phenyl)methanol (0.8883 g, 5.544 mmol) from Example 4 was added. The opaque yellow mixture was stirred at ambient temperature overnight (12 h). Aqueous NH.sub.3/NH.sub.4Cl (60 mL) was added to quench the reaction and the mixture was extracted with diethyl ether. The ether was dried over sodium sulfate, filtered, and solvent removed in vacuo. The product was purified by column chromatography (SiO.sub.2; hexanes/ethyl acetate 4:1).

[0182] .sup.1H NMR (400 MHz, C.sub.6D.sub.6): ? 7.46 (m, 2H, ArH), 7.28-7.18 (m, 1H ArH), 7.13-6.73 (m, 5H ArH), 4.35 (d, J=5.7 Hz, 2H, CH.sub.2.sup.7), 2.80 (t, J=7.5 Hz, 2H, CH.sub.2.sup.8), 2.53 (t, J=7.5 Hz, 2H, CH.sub.2.sup.9), 0.83 (t, J=5.7 Hz, 1H, OH).

[0183] .sup.13C NMR (101 MHz, C.sub.6D.sub.6): ? 139.3, 139.1, 129.8, 128.7, 128.6, 128.0, 127.9, 126.8, 124.6, 90.2, 82.1, 63.1, 31.7, 21.6.

Example 6Synthesis of W(CCH.SUB.2.CH.SUB.2.C.SUB.6.H.SUB.4.-o-CH.SUB.2.O)(CH.SUP.t.Bu)(O-2,6-.SUP.i.Pr.SUB.2.C.SUB.6.H.SUB.3.)

[0184] ##STR00023##

[0185] A round bottom flask equipped with stir bar and pressure equalizing dropping funnel was charged with W(C.sup.tBu)(CH.sub.2.sup.tBu)(O-2,6-.sup.iPr.sub.2C.sub.6H.sub.3).sub.2 (0.208 g, 0.306 mmol) and 5 mL of benzene. A solution of the (2-(4-phenylbut-3-yn-1-yl)phenyl)methanol (0.072 g, 0.304 mmol) prepared in Example 5 in 5 mL benzene was added dropwise via addition funnel with stirring. After stirring for 18 h the volatiles were removed in vacuo. Pentane, 4 mL, was added to the resulting dark viscous residue. The resulting suspension was filtered, and the pale-yellow solid was washed three times with pentane and dried in vacuo. Crystals suitable for single-crystal x-ray analysis were obtained by dissolving the product in warm benzene leaving the solution to sit undisturbed.

[0186] .sup.1H NMR (400 MHz, C.sub.6D.sub.6): ? 7.71-7.63 (m, 1H), 7.32 (dd, J=7.8, 1.7 Hz, 1H), 7.20 (dd, J=7.5, 1.8 Hz, 1H), 7.07 (t, J=7.6 Hz, 1H), 7.02-6.89 (m, 2H), 6.86-6.68 (m, 3H), 6.09-5.84 (m, 3H), 3.88-3.84 (m, 1H), 3.70-3.61 (m, 1H), 3.58-3.37 (m, 2H), 3.20-3.07 (m, 1H), 2.14 (d, J=14.9 Hz, 1H), 2.08-2.03 (m, 1H), 1.90 (d, J=14.7 Hz, 1H), 1.69 (d, J=7.0 Hz, 3H), 1.64 (d, J=3.9 Hz, 2H), 1.58 (d, J=4.2 Hz, 1H), 1.51 (d, J=6.7 Hz, 3H), 1.36 (d, J=6.9 Hz, 4H), 1.27 (d, J=6.8 Hz, 3H), 1.07 (s, 9H).

[0187] .sup.1H.sup.13C gHSQC, gHMBC spectra (400 MHz, C.sub.6D.sub.6): ? 286.7, 165.0, 164.0, 142.2, 140.6, 136.2, 136.0, 132.4, 131.1, 130.0, 129.8, 128.7, 126.8, 123.0, 122.8, 85.9, 84.9, 79.1, 46.1, 36.6, 35.7, 35.2, 34.3, 33.7, 33.5, 27.5, 26.5, 26.3, 24.9, 24.8, 24.6, 24.4, 21.5, 20.5 132.6, 130.2, 128.8, 126.9, 122.8, 122.5, 86. 78.8, 46.1, 36.7, 36.6, 34.2, 33.5, 27.5.

[0188] The 1-D NOESY/EXSY (500 MHz, toluene-d.sub.8) spectrum is shown in FIG. 2 (bottom), presented for comparison with the .sup.1H NMR spectrum (top), collected at 80? C. FIG. 2 demonstrates that W(C.sup.tBu)(CH.sub.2.sup.tBu)(O-2,6-.sup.iPr.sub.2C.sub.6H.sub.3).sub.2 is dynamic in solution. Further, the X-ray structure (FIG. 3) of the product shows that in the solid state, the W(C.sup.tBu)(CH.sub.2.sup.tBu)(O-2,6-.sup.iPr.sub.2C.sub.6H.sub.3).sub.2 is a dimer, binding through the bridging alkoxides from the cyclic ligand. In FIG. 3, ligand and solvent disorder parts and hydrogen atoms are removed for clarity.

Example 7Polymerization of Alkenes and Alkynes

[0189] In a nitrogen atmosphere glovebox, a scintillation vial equipped with a stir bar was charged with 3,8-didodecyloxy-5,6-dihydro-11,12-didehydrodibenzo[a,e]-[8]annulen (0.040 g, 0.069 mmol) and 2.0 mL of dry toluene. To this solution was added, in one portion, 0.40 mL of a 3.45 mM toluene stock solution of W(CCH.sub.2CH.sub.2C.sub.6H.sub.4-o-CH.sub.2O)(CH.sup.tBu)(O-2,6-.sup.iPr.sub.2C.sub.6H.sub.3) as prepared in Example 6, with stirring. After 27 m, 2.0 mL of dry toluene were added and the polymer was precipitated in 15 mL methanol with stirring. The polymer was isolated via filtration and washed with additional methanol and dried.

[0190] .sup.1H NMR (500 MHz, CDCl.sub.3): ? 7.40 (d, J=8.4 Hz, 2H), 6.69 (d, J=2.7 Hz, 2H), 6.64 (dd, J=8.4, 2.6 Hz, 2H), 3.71 (t, J=6.5 Hz, 4H), 3.21 (s, 4H), 1.60-1.70 (m, 4H), 1.15-1.45 (m, 36H), 0.87 (t, J=7.0 Hz, 6H).

[0191] Stacked .sup.1H NMR (C.sub.6D.sub.6, 500 MHz, 25? C.) spectra are shown in FIG. 4, including W(CCH.sub.2CH.sub.2C.sub.6H.sub.4-o-CH.sub.2O)(CH.sup.tBu)(O-2,6-.sup.iPr.sub.2C.sub.6H.sub.3), (bottom), 3,8-didodecyloxy-5,6-dihydro-11,12-didehydrodibenzo[a,e]-[8]annulen (2.sup.nd from the bottom), and polymerization progress (top 3 spectra).

Example 8General Conditions for Polymerization of Alkenes and Alkynes

[0192] In a nitrogen atmosphere glovebox, scintillation vials equipped with stir bars were charged with 3,8-didodecyloxy-5,6-dihydro-11,12-didehydrodibenzo[a,e]-[8]annulen (15 mg, 0.026 mmol) and 1.0 mL of dry toluene. To these solutions, 100.0 ?L of a 5.18 mM toluene stock solution of W(CCH.sub.2CH.sub.2C.sub.6H.sub.4-o-CH.sub.2O)(CH.sup.tBu)(O-2,6-.sup.iPr.sub.2C.sub.6H.sub.3) as prepared in Example 6, was added in one portion with stirring. The vials were sealed and mixed. After the appropriate reaction time, the vials were removed from the glovebox, unsealed and quenched with methanol, 10-12 mL. The polymers were isolated via filtration, washed with additional methanol and dried overnight under vacuum.

[0193] The experiment was performed in two separate runs; entries 1-4 were performed in one run while entries 5-9 were performed separately. Reaction times and yields are listed in Table 1.

TABLE-US-00001 TABLE 1 Reaction times and yields for the synthesis of cyclic poly-(o-phenylene ethynylene) with W(CCH.sub.2CH.sub.2C.sub.6H.sub.4-o- CH.sub.2O)(CH.sup.tBu)(O-2,6-.sup.iPr.sub.2C.sub.6H.sub.3). Entry Reaction Time.sup.a Isolated yield Percent yield.sup.b c-PoPE-1 10 14.1 mg 94% c-PoPE-2 10 10.7 mg 9.8% c-PoPE-3 5 9.9 mg 17% c-PoPE-4 2 6.5 mg 7.2% c-PoPE-5 25 14 mg 73% c-PoPE-6 15 13 mg 86% c-PoPE-7 10 12 mg 80% c-PoPE-8 5 13 mg 86% c-PoPE-9 2 11 mg 93% .sup.aTime reported in minutes. .sup.bDetermined from isolated yield.

[0194] Thus, Example 8 demonstrates general preparation conditions for preparing a cyclic polymer according to the disclosure. The catalysts and polymers of the disclosure are further characterized in Example 9.

Example 9Polymerization of Alkenes and Alkynes with W(CCMe.SUB.3.)(OCMe.SUB.3.).SUB.3

[0195] Additionally, the polymerization of 3,8-didodecyloxy-5,6-dihydro-11,12-didehydrodibenzo[a,e]-[8]annulen was investigated with commercially-available W(CCMe.sub.3)(OCMe.sub.3).sub.3, following a similar procedure as Example 8.

[0196] In a nitrogen atmosphere glovebox, a scintillation vial equipped with a stir bar was charged with 3,8-didodecyloxy-5,6-dihydro-11,12-didehydrodibenzo[a,e]-[8]annulen (15 mg, 0.026 mmol) and 1.0 mL of dry toluene. To this solution 100.0 ?L of a 5.29 mM toluene stock solution of W(CCMe.sub.3)(OCMe.sub.3).sub.3 was added in one portion with stirring. The vial was sealed and mixed. The vial was removed from the glovebox, unsealed and quenched by adding methanol, 10-12 mL after 5 minutes. The polymer was isolated via filtration, washed with additional methanol and dried overnight under vacuum. The results from the W(CCMe.sub.3)(OCMe.sub.3).sub.3 compound (I-PoPE) were compared with the results obtained for catalysts of the disclosure, (c-PoPE) and are presented in Table 2.

##STR00024##

TABLE-US-00002 TABLE 2 Catalysis conditions and characterization data for the synthesis of cyclic and linear poly-(o-phenylene ethynylene). Entry Time.sup.a Mn.sup.b ?.sup.b DP.sub.n %.sup.d c-PoPE-1 10 10,900 4.76 18 100 c-PoPE-2 10 25,100 2.68 43 13 c-PoPE-3 5 19,400 2.28 33 29 c-PoPE-4 2 11,900 2.54 50 12 I-PoPE.sup.c-1 5 19,600 2.75 34 100 c-PoPE-5 25 54,664 2.21 95 c-PoPE-6 15 56,837 3.00 99 c-PoPE-7 10 43,366 3.19 76 c-PoPE-8 5 61,290 2.39 107 c-PoPE-9 2 44,729 1.60 253 I-PoPE.sup.c-2 5 62,012 2.07 108 .sup.aMinutes, .sup.bDetermined (g/mol) by size-exclusion chromatography (SEC) equipped with differential refractive index (DRI) and viscometry using dichlorobenzene (DCB) as the mobile phase at 140? C. .sup.cLinear generated using W(CCME.sub.3)(OCMe.sub.3).sub.3. .sup.d% conversion of 3,8-didocdecyloxy-5,6-dihydro-11,12-didehydrodibonzo[a,e]-[8]annulen.

[0197] Solution properties of cyclic poly-(o-phenylene ethynylene) were compared with those of linear poly-(o-phenylene ethynylene) via GPC analysis, providing evidence on the polymer cyclic topology. With a smaller hydrodynamic volume, cyclic polymers are expected to elute later than their linear counterparts, for a given molecular weight. As shown in the plot of log MW versus elution volume (FIGS. 5 and 6), for each set of collected data, polymers prepared with catalysts of the invention generally follow this trend. Thus, the data in FIGS. 5 and 6 suggests preparation of high molecular weight cyclic polymers with catalysts of the invention.

[0198] Formation of cyclic poly-(o-phenylene ethynylene) was confirmed by analyzing the intrinsic viscosity of the prepared poly-(o-phenylene ethynylene) in THF using a viscometer-equipped GPC. Due to their smaller overall dimensions, cyclic polymers are expected to exhibit lower intrinsic viscosity compared with analogous linear polymers for a given molecular weight. As shown in the Mark-Houwink-Sakurada plots in FIGS. 7 and 8 where log [n] was plotted vs log M, where [n] was the intrinsic viscosity and M was the viscosity-average molar mass, most of the polymers prepared with the catalyst of the disclosure follow this trend.

[0199] Additionally, as shown in the plots of mean square radius of gyration (<R.sub.g.sup.2>) versus molar mass (FIGS. 9 and 10) for the prepared poly-(o-phenylene ethynylene), for each set of collected data, most of the polymers prepared with the catalyst of the disclosure exhibit lower mean square radii of gyration than the analogous polymer prepared with a catalyst not of the disclosure.

[0200] However, one entry from both runs of Example 8 (c-PoPE-1 and c-PoPE-7) are outliers that do not follow the trend. In the case of these polymers, the generated poly-(o-phenylene ethynylene) had greater intrinsic viscosity than the linear analogue, as shown on the Mark-Houwink-Sakurada plots (FIGS. 7 and 8), as well as a higher mean square radius of gyration than the linear analogue, as shown in FIGS. 9 and 10. Without intending to be bound by theory, it is believed that the polymerization conditions for c-PoPE-1 and c-PoPE-7 can be optimized to produce a polymer with an intrinsic viscosity consistent with the cyclic analogues, for example, by optimizing reaction conditions such as admixing time prior to quenching the solution, as well as the supply of monomer, i.e. constant flow or batch fed addition of monomer, can be further optimized to improve polymerization.

[0201] Thus, Example 9 demonstrates preparation of cyclic polymers using a catalyst of the disclosure and linear polymers using a catalyst not of the disclosure.

Tethered Alkylidyne and Methods of Making the Same

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Abstract

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