METAL COMPLEXES HAVING 4-H,6-H OR 8-H DIHYDROAZULENYL LIGANDS AND USE THEREOF
20240317779 ยท 2024-09-26
Assignee
Inventors
Cpc classification
B01J31/1616
PERFORMING OPERATIONS; TRANSPORTING
C07F9/5045
CHEMISTRY; METALLURGY
C07F17/02
CHEMISTRY; METALLURGY
International classification
C07F15/00
CHEMISTRY; METALLURGY
Abstract
The invention relates to a method for preparing compounds of the general formula M.sup.AY.sub.n(AzuH) (I), where M.sup.A=alkali metal, Y=neutral ligand, n=0, 1, 2, 3, or 4. AzuH is azulene (bicyclo[5.3.0]decapentaene) or an azulene derivative that bears a hydride anion H? in the 4, 6 or 8 position in addition to an H atom. The invention additionally provides compounds obtainable by this method, and a method using such compounds for preparation of complexes of metals of groups 6 to 12. The invention further relates to complexes of middle and later transition metals (groups 6 to 12) which each have at least one H-dihydroazulenyl anion (AzuH).sup.1?, and to the use of all the aforementioned transition metal complexes as precatalysts or catalysts or electron transfer reagents in a chemical reaction or as precursor compounds for production of a layer containing a metal M, or of a metal layer consisting of the metal M, especially on at least one surface of a substrate. The invention also provides a substrate obtainable by such a method. 25
Claims
1. A method for preparing compounds of the general formula
M.sup.AY.sub.n(AzuH)(I), wherein M.sup.A is an alkali metal, Y is a neutral ligand which is bonded or coordinated to M.sup.A via at least one donor atom, wherein H.sub.2O is excluded, n=0, 1, 2, 3, or 4 and AzuH=azulene or an azulene derivative that bears a hydride anion in the 4, 6 or 8 position in addition to an H atom, wherein Azu=azulene according to the formula ##STR00013## or Azu=an azulene derivative having an azulene scaffold according to formula II consisting of a five-membered ring and a seven-membered ring, wherein a) at least one carbon atom of the azulene scaffold selected from the group consisting of the carbon atoms C1, C2, C3, C4, C5, C6, C7 and C8, bears a substituent R.sup.F wherein the substituents R.sup.F are selected independently of one another from the group consisting of primary, secondary, tertiary alkyl, alkenyl and alkynyl radicals having 1 to 10 carbon atoms, cyclic alkyl radicals having 3 to 10 carbon atoms, a benzyl radical, a mononuclear or polynuclear arene and a mononuclear or polynuclear heteroarene, wherein two substituents R.sup.F can optionally form a ring, and b) at least one carbon atom of the azulene scaffold, selected from the group consisting of the carbon atoms C4, C6 and C8, bears an H atom, comprising the following steps: A. providing i. azulene or an azulene derivative having an azulene scaffold according to formula II consisting of a five-membered ring and a seven-membered ring, wherein at least one carbon atom of the azulene scaffold selected from the group consisting of the carbon atoms C1, C2, C3, C4, C5, C6, C7 and C8, bears a substituent R.sup.F wherein the substituents R.sup.F are selected independently of one another from the group consisting of primary, secondary, tertiary alkyl, alkenyl and alkynyl radicals having 1 to 10 carbon atoms, cyclic alkyl radicals having 3 to 10 carbon atoms, a benzyl radical, a mononuclear or polynuclear arene and a mononuclear or polynuclear heteroarene, wherein two substituents R.sup.F can optionally form a ring, and at least one carbon atom of the azulene scaffold, selected from the group consisting of the carbon atoms C4, C6 and C8, bears an H atom, and ii. at least one hydridic reducing agent Z, B. reacting the azulene or the azulene derivative with the at least one hydride reducing agent Z in a solvent S.sub.P, and when using at least one alkali metal aluminum tetrahydride M.sup.AAlH.sub.4 as a first hydride reducing agent Z.sub.1 C. providing i. at least one second hydride reducing agent Z.sub.2 selected from the group consisting of alkali metal hydrides M.sup.AH and/or ii. at least one electron pair donor E, wherein the electron pair donor E has at least one donor atom, wherein H.sub.2O is excluded, and D. optionally adding a neutral ligand Y, if Y is not equal to S.sub.P and Y is not equal to E.
2. The method according to claim 1, wherein at least one hydride reducing agent Z is selected from the group consisting of alkali metal hydrides M.sup.AH, alkali metal borotetrahydrides M.sup.ABH.sub.4, alkali metal trialkylborohydrides M.sup.A[(R).sup.C).sub.3BH], alkali metal aluminum tetrahydrides M.sup.AAlH.sub.4, alkali metal trialkylaluminum hydrides M.sup.A[(R).sup.D).sub.3AlH], alkali metal dihydrido-bis(dialkoxy)aluminates M.sup.A[AlH.sub.2(OR.sup.E).sub.2], and mixtures thereof, wherein i. the radicals R.sup.C and R.sup.D are each selected independently of one another from the group consisting of primary, secondary, tertiary alkyl, alkenyl and alkynyl radicals having 1 to 10 carbon atoms, wherein in each case two substituents R.sup.C or two substituents R.sup.D can optionally form a ring, and ii. the radicals OR.sup.E are each independently of one another a corresponding base of a glycol ether R.sup.EOH.
3. The method according to claim 2, wherein the glycol ethers R.sup.EOH are independently selected from the group consisting of monooxomethylene monoethers, monoethylene glycol monoethers, monopropylene glycol monoethers, and mixtures of isomers thereof, and mixtures thereof.
4. The method according to claim 1, wherein the solvent S.sub.P and the neutral ligand Y and/or the neutral ligand Y and the electron pair donor E and/or the solvent S.sub.P and the electron pair donor E are miscible or identical.
5. The method according to claim 1, wherein the electron pair donor E is a base selected from the group consisting of organic, organometallic and inorganic bases, and mixtures thereof.
6. The method according to claim 1, wherein in step A. an azulene derivative is provided, wherein at least on the carbon atoms C4 and C6 or on the carbon atoms C8 and C6 or on the carbon atom C4 and/or on the carbon atom C8 of the azulene skeleton, an H atom is provided.
7. The method according to claim 1, wherein after the reaction in step B. or after step C., a step is carried out which comprises isolation of M.sup.AY.sub.n(AzuH) (I): as a suspension or solution comprising M.sup.AY.sub.n(AzuH) (I) and at least one solvent S.sub.P, or as a liquid or solid.
8. A solution or suspension comprising M.sup.AY.sub.n(AzuH) (I) and at least one solvent S.sub.P, obtained or obtainable by a method according to claim 1.
9. Compounds of the general formula M.sup.AY.sub.n(AzuH) (I), obtained or obtainable by a method according to claim 1.
10. Compounds of the general formula M.sup.AY.sub.n(AzuH) (I), wherein M.sup.A is an alkali metal, Y is a neutral ligand which is bonded or coordinated to M.sup.A via at least one donor atom, wherein H.sub.2O is excluded, n=0, 1, 2, 3, or 4 and AzuH=azulene or an azulene derivative that bears a hydride anion in the 4, 6 or 8 position in addition to an H atom, wherein Azu=azulene according to the formula ##STR00014## or Azu=an azulene derivative having an azulene scaffold according to formula II consisting of a five-membered ring and a seven-membered ring, wherein a) at least one carbon atom of the azulene scaffold selected from the group consisting of the carbon atoms C1, C2, C3, C4, C5, C6, C7 and C8, bears a substituent R.sup.F wherein the substituents R.sup.F are selected independently of one another from the group consisting of primary, secondary, tertiary alkyl, alkenyl and alkynyl radicals having 1 to 10 carbon atoms, cyclic alkyl radicals having 3 to 10 carbon atoms, a benzyl radical, a mononuclear or polynuclear arene and a mononuclear or polynuclear heteroarene, wherein two substituents R.sup.F can optionally form a ring, and b) at least one carbon atom of the azulene scaffold, selected from the group consisting of the carbon atoms C4, C6 and C8, bears an H atom, wherein the compounds Li(O(C.sub.2H.sub.5).sub.2).sub.n(AzulenH) and Li(O(C.sub.2H.sub.5).sub.2).sub.n(GuaH), wherein n=0, 1 or 2, AzulenH=azulene that bears a hydride anion in the 4, 6 or 8 position in addition to an H atom, GuaH=7-isopropyl-1,4-dimethyl-8-H-dihydroazulene are excluded.
11. Compounds according to claim 10, wherein Azu=an azulene derivative and the compound of the general formula M.sup.AY.sub.n(AzuH) (I) is isomerically pure.
12. Compounds according to claim 10, wherein Azu=an azulene derivative, and wherein at least the carbon atoms C1, C4 and C7 of the azulene skeleton bear a substituent R.sup.F, and isomers thereof.
13. Compounds according to claim 10, wherein the alkali metal M.sup.A is selected from the group consisting of Li, Na and K.
14. Compounds according to claim 10, wherein the neutral ligand Y is a) an aprotic polar solvent or b) a crown ether which is selected from the group consisting of macrocyclic polyethers and the aza-, phospha- and thia-derivatives thereof, wherein an inner diameter of the crown ether and an ion radius of M.sup.A correspond to each other.
15. Compound according to claim 10, having the formula ##STR00015## where M.sup.A is an alkali metal, in particular selected from the group Li, Na or K.
16. A method for preparing metal complexes of the general formula
M(L.sub.K).sub.f(AzuH).sub.m(III)
or
M(L.sub.N)(AzuH).sub.q(IV)
or
[M(L.sub.S).sub.g(AzuH).sub.v]X(V)
or
[M(L.sub.T)(AzuH).sub.z]X(VI), wherein M=central metal atom selected from group 6, group 7, group 8, group 9, group 10, group 11, or group 12, L.sub.K=optional neutral sigma donor ligand or optional neutral pi donor ligand, f=number of L.sub.K ligands, where f=0, 1, 2, 3, 4, 5, or 6, AzuH=azulene or an azulene derivative that bears a hydride anion in the 4, 6 or 8 position in addition to an H atom, m=number of AzuH ligands, where m=1, 2, 3, 4, 5, 6, or 7, L.sub.N=at least one anionic sigma donor ligand or at least one anionic pi donor ligand, where a sum u of the negative charges of all L.sub.N ligands is ?1, ?2, ?3, ?4, ?5 or ?6, q=number of AzuH ligands, where q=w.sub.2?|u|, where w.sub.2>|u| and w.sub.2=2, 3, 4, 5, 6, or 7, and where |u| is an absolute value of the sum of the negative charges of all L.sub.N ligands, where |u|=1, 2, 3, 4, 5, or 6, L.sub.S=optional neutral sigma donor ligand or optional neutral pi donor ligand, g=number of L.sub.S ligands, where g=0, 1, 2, 3, 4, 5, or 6, v=number of AzuH ligands, where v=w.sub.3?1, where w.sub.3=2, 3, 4, 5, 6, or 7, L.sub.T=at least one anionic sigma donor ligand or at least one anionic pi donor ligand, where a sum h of the negative charges of all L.sub.T ligands is ?1, ?2, ?3, ?4 or ?5, z=number of AzuH ligands, where z=w.sub.4?(|h|+1), where w.sub.4>(|h|+1) and w.sub.4=3, 4, 5, 6, or 7, and where |h| is an absolute value of the sum of the negative charges of all L.sub.T ligands, where |h|=1, 2, 3, 4, or 5, X.sup.?=halide anion or monovalent weakly coordinating anion or monovalent non-coordinating anion, wherein Azu=azulene according to the formula ##STR00016## or Azu=an azulene derivative which has an azulene skeleton according to formula II, consisting of a five-membered ring and a seven-membered ring, wherein a) at least one carbon atom of the azulene scaffold selected from the group consisting of the carbon atoms C1, C2, C3, C4, C5, C6, C7 and C8, bears a substituent R.sup.F wherein the substituents R.sup.F are selected independently of one another from the group consisting of primary, secondary, tertiary alkyl, alkenyl and alkynyl radicals having 1 to 10 carbon atoms, cyclic alkyl radicals having 3 to 10 carbon atoms, a benzyl radical, a mononuclear or polynuclear arene and a mononuclear or polynuclear heteroarene, wherein two substituents R.sup.F can optionally form a ring, and b) at least one carbon atom of the azulene scaffold, selected from the group consisting of the carbon atoms C4, C6 and C8, bears an H atom, using a compound according to claim 1 having the general formula M.sup.AY.sub.n(AzuH) (I), or a solution or a suspension, comprising a compound of the general formula M.sup.AY.sub.n(AzuH) (I) and at least one solvent S.sub.P, wherein M.sup.A is an alkali metal, Y is a neutral ligand which is bonded or coordinated to M.sup.A via at least one donor atom, wherein H.sub.2O is excluded, n=0, 1, 2, 3, or 4 and AzuH and Azu are as defined above, comprising the steps of: A. providing the compound of the general formula M.sup.AY.sub.n(AzuH) (I) or the solution or the suspension comprising the compound of the general formula M.sup.AY.sub.n(AzuH) (I) and the at least one solvent S.sub.P, and B. synthesis of the metal complex
M(L.sub.K).sub.f(AzuH).sub.m(III)
or
M(L.sub.N)(AzuH).sub.q(IV)
or
[M(L.sub.S).sub.g(AzuH).sub.v]X(V)
or
[M(L.sub.T)(AzuH).sub.z]X(VI) using the compound according to the general formula M.sup.AY.sub.n(AzuH) (I) as reactant.
17. The method according to claim 16, wherein the synthesis in step B comprises at least one salt metathesis reaction and/or at least one oxidation reaction.
18. The method according to claim 16, wherein M is selected from the group consisting of chromium, molybdenum, tungsten, manganese, technetium, rhenium, iron, ruthenium, osmium, cobalt, rhodium, iridium, nickel, palladium, platinum, copper, silver, gold, zinc, cadmium, and mercury.
19. The method according to claim 16, wherein the ligands L.sub.K and L.sub.S are independently selected from the group consisting of monodentate and polydentate phosphorus donor ligands, alkenes, cyclic dienes and cyclic polyenes, and mononuclear arenes, polynuclear arenes, mononuclear heteroarenes and polynuclear heteroarenes, and derivatives thereof, and/or the ligand L.sub.N is a monoanionic ligand selected from the group consisting of anions of cyclopentadiene and derivatives thereof, alkyl anions, aryl anions and a fluoride anion and/or the ligand L.sub.T is a monoanionic ligand selected from the group consisting of anions of cyclopentadiene and derivatives thereof and a fluoride anion, or a dianionic ligand.
20. Metal complexes of the general formula
M(L.sub.K).sub.f(AzuH).sub.m(III)
or
M(L.sub.N)(AzuH).sub.q(IV)
or
[M(L.sub.S).sub.g(AzuH).sub.v]X(V)
or
[M(L.sub.T)(AzuH).sub.z]X(VI), or solutions or suspensions comprising a metal complex of the general formula
M(L.sub.K).sub.f(AzuH).sub.m(III)
or
M(L.sub.N)(AzuH).sub.q(IV)
or
[M(L.sub.S).sub.g(AzuH).sub.v]X(V)
or
[M(L.sub.T)(AzuH).sub.z]X(VI) and at least one solvent which is miscible with or identical to the solvent Sp, wherein M=central metal atom selected from group 6, group 7, group 8, group 9, group 10, group 11, or group 12, L.sub.K=optional neutral sigma donor ligand or optional neutral pi donor ligand, f=number of L.sub.K ligands, where f=0, 1, 2, 3, 4, 5, or 6, AzuH=azulene or an azulene derivative that bears a hydride anion in the 4, 6 or 8 position in addition to an H atom, m=number of AzuH ligands, where m=1, 2, 3, 4, 5, 6, or 7, L.sub.N=at least one anionic sigma donor ligand or at least one anionic pi donor ligand, where a sum u of the negative charges of all L.sub.N ligands is ?1, ?2, ?3, ?4, ?5 or ?6, q=number of AzuH ligands, where q=w.sub.2?|u|, where w.sub.2>|u| and w.sub.2=2, 3, 4, 5, 6, or 7, and where |u| is an absolute value of the sum of the negative charges of all L.sub.N ligands, where |u|=1, 2, 3, 4, 5, or 6, L.sub.S=optional neutral sigma donor ligand or optional neutral pi donor ligand, g=number of L.sub.S ligands, where g=0, 1, 2, 3, 4, 5, or 6, v=number of AzuH ligands, where v=w.sub.3?1, where w.sub.3=2, 3, 4, 5, 6, or 7, L.sub.T=at least one anionic sigma donor ligand or at least one anionic pi donor ligand, where a sum h of the negative charges of all L.sub.T ligands is ?1, ?2, ?3, ?4 or ?5, z=number of AzuH ligands, where z=w.sub.4?(|h|+1), where w.sub.4>(|h|+1) and w.sub.4=3, 4, 5, 6, or 7, and where |h| is an absolute value of the sum of the negative charges of all L.sub.T ligands, where |h|=1, 2, 3, 4, or 5, X.sup.?=halide anion or monovalent weakly coordinating anion or monovalent non-coordinating anion, wherein Azu=azulene according to the formula ##STR00017## or Azu=an azulene derivative which has an azulene skeleton according to formula II, consisting of a five-membered ring and a seven-membered ring, wherein a) at least one carbon atom of the azulene scaffold selected from the group consisting of the carbon atoms C1, C2, C3, C4, C5, C6, C7 and C8, bears a substituent R.sup.F wherein the substituents R.sup.F are selected independently of one another from the group consisting of primary, secondary, tertiary alkyl, alkenyl and alkynyl radicals having 1 to 10 carbon atoms, cyclic alkyl radicals having 3 to 10 carbon atoms, a benzyl radical, a mononuclear or polynuclear arene and a mononuclear or polynuclear heteroarene, wherein two substituents R.sup.F can optionally form a ring, and b) at least one carbon atom of the azulene scaffold, selected from the group consisting of the carbon atoms C4, C6 and C8, bears an H atom, obtained or obtainable according to a method according to claim 15.
21. Metal complexes of the general formula
M(L.sub.K).sub.f(AzuH).sub.m(III)
or
M(L.sub.N)(AzuH).sub.q(IV)
or
[M(L.sub.S).sub.g(AzuH).sub.v]X(V)
or
[M(L.sub.T)(AzuH).sub.z]X(VI) wherein M=central metal atom selected from group 6, group 7, group 8, group 9, group 10, group 11, or group 12, L.sub.K=optional neutral sigma donor ligand or optional neutral pi donor ligand, f=number of L.sub.K ligands, where f=0, 1, 2, 3, 4, 5, or 6, AzuH=azulene or an azulene derivative that bears a hydride anion in the 4, 6 or 8 position in addition to an H atom, m=number of AzuH ligands, where m=1, 2, 3, 4, 5, 6, or 7, L.sub.N=at least one anionic sigma donor ligand or at least one anionic pi donor ligand, where a sum u of the negative charges of all L.sub.N ligands is ?1, ?2, ?3, ?4, ?5 or ?6, q=number of AzuH ligands, where q=w.sub.2?|u|, where w.sub.2>|u| and w.sub.2=2, 3, 4, 5, 6, or 7, and where |u| is an absolute value of the sum of the negative charges of all L.sub.N ligands, where |u|=1, 2, 3, 4, 5, or 6, L.sub.S=optional neutral sigma donor ligand or optional neutral pi donor ligand, g=number of L.sub.S ligands, where g=0, 1, 2, 3, 4, 5, or 6, v=number of AzuH ligands, where v=w.sub.3?1, where w.sub.3=2, 3, 4, 5, 6, or 7, L.sub.T=at least one anionic sigma donor ligand or at least one anionic pi donor ligand, where a sum h of the negative charges of all L.sub.T ligands is ?1, ?2, ?3, ?4 or ?5, z=number of AzuH ligands, where z=w.sub.4?(|h|+1), where w.sub.4>(|h|+1) and w.sub.4=3, 4, 5, 6, or 7, and where |h| is an absolute value of the sum of the negative charges of all L.sub.T ligands, where |h|=1, 2, 3, 4, or 5, X.sup.?=halide anion or monovalent weakly coordinating anion or monovalent non-coordinating anion, wherein Azu=azulene according to the formula ##STR00018## or Azu=an azulene derivative which has an azulene skeleton according to formula II, consisting of a five-membered ring and a seven-membered ring, wherein a) at least one carbon atom of the azulene scaffold selected from the group consisting of the carbon atoms C1, C2, C3, C4, C5, C6, C7 and C8, bears a substituent R.sup.F wherein the substituents R.sup.F are selected independently of one another from the group consisting of primary, secondary, tertiary alkyl, alkenyl and alkynyl radicals having 1 to 10 carbon atoms, cyclic alkyl radicals having 3 to 10 carbon atoms, a benzyl radical, a mononuclear or polynuclear arene and a mononuclear or polynuclear heteroarene, wherein two substituents R.sup.F can optionally form a ring, and b) at least one carbon atom of the azulene scaffold, selected from the group consisting of the carbon atoms C4, C6 and C8, bears an H atom, wherein the compound Fe(AzulenH).sub.2 and Cr(AzulenH).sub.2, and isomers thereof, are excluded.
22. Metal complex according to claim 20, comprising a metal complex and at least one solvent which is miscible with or identical to the solvent Sp, wherein the metal complex is selected from the group consisting of Fe(GuaH).sub.2, Ru(GuaH).sub.2, Ru(Cp*)(GuaH), [Ru(p-cymene)(GuaH)]PF.sub.6, Co(GuaH).sub.2, [Co(GuaH).sub.2]PF.sub.6, Rh(nbd)(GuaH), Rh(cod)(GuaH), [Rh(Cp*)(GuaH)]PF.sub.6, PtMe.sub.3(GuaH), [Pt(cod)(GuaH)]PF.sub.6, Cu(PPh.sub.3)(GuaH), Zn(GuaH).sub.2 and Zn(Mes)(GuaH).
23. A use of at least one metal complex according to claim 20, as a i. pre-catalyst or pre-catalyst-containing solution or suspension in a chemical reaction and/or ii. catalyst or catalyst-containing solution or suspension in a chemical reaction and/or iii. electron transfer reagent or solution or suspension containing electron transfer reagent in a chemical reaction and/or iv. precursor compound, or solution or suspension containing precursor compound, for preparing at least one layer containing a metal M, or at least one metal layer consisting of the metal M on at least one surface of a substrate.
24. A method for carrying out a chemical reaction using at least one metal complex according to claim 20, comprising the steps of: A) providing the at least one metal complex or the at least one solution or suspension comprising a metal complex and at least one solvent which is miscible with or identical to the solvent S.sub.p, and B) carrying out the chemical reaction using the at least one metal complex as a precatalyst, as a catalyst or as an electron transfer reagent.
25. A method for preparing i. at least one metal layer consisting of a metal M or ii. at least one layer containing a metal M, on at least one surface of a substrate using at least one metal complex according to claim 20, comprising the steps of: A) providing the at least one metal complex or the at least one solution or suspension comprising a metal complex and at least one solvent which is miscible with or identical to the solvent S.sub.p, and B) depositing i. the at least one metal layer consisting of the metal M or ii. the at least one layer containing the metal M, on the at least one surface of the substrate using the metal complex as precursor compound.
26. The method according to claim 1, where Azu=Gua=7-iso-propyl-1,4-dimethylazulene and AzuH=GuaH=7-iso-propyl-1,4-dimethyl-8-H-dihydroazulene.
Description
[0865] Other characteristics, details, and advantages of the invention follow from the exact wording of the claims, as well as from the following description of the embodiment examples based upon the illustrations. The following are shown:
[0866]
[0867]
[0868] The .sup.1H NMR spectra shown in
[0869] During the hydrosilylation reaction of 1-octene with pentamethylsiloxane using 5 ppm PtMe.sub.3(GuaH) as catalyst (cf. Example 15, NMR experiments with 5 ppm Pt), the .sup.1H NMR spectra shown in
[0870] The reaction equation for the hydrosilylation of 1-octene is as follows:
##STR00011##
[0871] In each case, the conversion was determined based on the CH.sub.2 group of the product (highlighted in gray in the product molecule) with a shift of 0.60 ppm. The calculation of the above conversions also took into account the .sup.1H NMR spectra recorded after approximately 0.50 h, 2 h, 4 h, and 24 h in C.sub.6D.sub.6 at 298 K and 300 MHz. Table 1 lists the calculated conversions of the hydrosilylation reaction of 1-octene with pentamethylsiloxane using 5 ppm PtMe.sub.3(GuaH) as catalyst (see column 2).
TABLE-US-00001 TABLE 1 Time in h Conversion in % 0 0.0 0.25 28.0 0.50 32.3 1 37.6 2 49.8 4 73.1 8 95.8 24 99.5 48 100.0
[0872] The graphical evaluation of the results listed in Table 2 is shown in
[0873] It can be concluded that the hydrosilylation reaction using 5 ppm PtMe.sub.3(GuaH) as catalyst is almost complete after about 8 h. Consequently, a satisfactory reaction rate is achieved.
[0874] Advantageously, the Pt(IV) compound PtMe.sub.3(GuaH) is present as a liquid and shows an absorption in the visible range. The latter is a further advantage of the Pt(IV) compound used here. This is because light-induced platinum-catalyzed hydrosilylation reactions regularly involve the use of UV-Vis light, which usually requires special safety measures to reduce the risk of skin cancer. Such safety measures are not mandatory when using PtMe.sub.3(GuaH).
[0875] According to the established teaching, photolysis of a known catalyst containing a cyclopentadienyl anion, such as CpPtMe.sub.3 and (MeCp)PtMe.sub.3, in the presence of a silane, such as pentamethylsiloxane, leads to the formation of a platinum colloid as active hydrosilylation catalyst. (L. D. Boardman, Organometallics 1992, 11, 4194-4201) Boardman gives a catalyst concentration of 10 ppm platinum as CpPtMe.sub.3 for the hydrosilylation reaction of 1-octene with pentamethylsiloxane (equimolar mixture).
[0876] When using the precatalyst PtMe.sub.3(GuaH) presented for the first time in the present invention, complete conversion of the substrates 1-octene and pentamethylsiloxane is observed already at 50% of the catalyst concentration chosen in the literature, i.e., at a catalyst concentration of 5 ppm platinum as PtMe.sub.3(GuaH).
[0877] A further advantage of the compound PtMe.sub.3(GuaH) used here as a precatalyst over Pt(IV) compounds containing cyclopentadienyl anions consists in the fact that the guaiazulene required for the preparation thereof is synthesized using renewable raw materials instead of petroleum. As a result, the preparation of the Pt(IV) complex PtMe.sub.3(GuaH) can be achieved in a comparatively sustainable, simple and inexpensive manner.
[0878] Consequently, the half-sandwich complex PtMe.sub.3(GuaH) used in the context of the present invention as a precatalyst for the hydrosilylation reaction of 1-octene with pentamethylsiloxane constitutes a relatively sustainable and cost-effective alternative to previously known hydrosilylation catalysts such as CpPtMe.sub.3 and (MeCp)PtMe.sub.3.
[0879] Operating procedures for synthesis of Li(GuaH), Na([15]-crown-5)(GuaH), K([18]-crown-6)(GuaH), Fe(GuaH).sub.2, Ru(GuaH).sub.2, Ru(Cp*)(GuaH), [Ru(p-cymene)(GuaH)]PF.sub.6, Co(GuaH).sub.2, [Co(GuaH).sub.2]PF.sub.6, Rh(nbd)(GuaH), Rh(cod)(GuaH), [Rh(Cp*)(GuaH)]PF.sub.6, PtMe.sub.3(GuaH), [Pt(cod)(GuaH)]PF.sub.6, Cu(PPh.sub.3)(GuaH), Zn(GuaH).sub.2 and Zn(Mes)(GuaH)
[0880] (GuaH).sup.?=7-iso-propyl-1,4-dimethyl-8-H-dihydroazulenyl, C.sub.15H.sub.19.sup.?
[0881] Cp*=1,2,3,4,5-pentamethylcyclopentadienyl, C.sub.5Me.sub.5.sup.?
Materials and Methods
[0882] All reactions were carried out in a standard inert gas atmosphere. The solvents and reagents used were purified and dried according to standard procedures. In the case of reagents which were used as solutions, the contents were determined by titration or ICP-MS/OES.
[0883] All nuclear magnetic resonance spectroscopic measurements were carried out using a Bruker AV II 300, Bruker AV II HD 300, DRX 400, or AV III 500 instrument. .sup.13C NMR spectra were measured as standard using .sup.1H broadband decoupling at 300 K. .sup.1H and .sup.13C-NMR spectra were calibrated to the corresponding residual proton signal of the solvent as an internal standard: .sup.1H: DMSO[d.sub.6]: 2.50 ppm; .sup.13C: DMSO[d.sub.6]: 39.52 ppm. The chemical shifts are indicated in ppm and refer to the 6 scale. All signals are given the following abbreviations according to their splitting pattern: s (singlet), d (doublet), t (triplet), q (quartet), sept (septet), m (multiplet), br (broad signal).
[0884] In substance, the measurements of infrared spectra were usually performed on an Alpha ATR-IR spectrometer made by Bruker. The absorption bands are indicated in wave number (cm.sup.?1), and the intensity is described with the following abbreviations: w (weak), m (medium strong), st (strong), vst (very strong), br (broad). The spectra were always normalized to the band with the highest intensity.
[0885] High-resolution LIFDI mass spectra were obtained using an AccuTOF GCv-TOF mass spectrometer (JEOL).
[0886] The elemental analyses were carried out on a vario MICRO cube combustion device made by Elementar. Sample preparation was carried out in a glove box flooded with nitrogen by weighing the substance in tin crucibles, which were cold-welded and stored in a protective gas atmosphere until measurement. The elements of hydrogen, carbon and nitrogen were determined by means of a combustion analysis, wherein the information is always given in mass percent.
[0887] Data collection for crystal structure analysis was carried outed using a Stoe Stadivari diffractometer or a Bruker D8 Quest diffractometer by the Department of Chemistry, University of Marburg, Germany. After the solution process (SHELXT) and refinement process (SHELXL 2017/1), the data were validated using Platon. The molecular structures were graphically illustrated using Diamond 4.
Example 1: Preparation of Li(GuaH)
[0888] ##STR00012##
[0889] Method A. Guaiazulene (5.00 g, 25.0 mmol, 1.00 eq.) and lithium triethylborohydride (1.7 M in THF) (15 mL, 25.5 mmol, 1.02 eq.) were added to a flask flooded with argon gas, and the solvent was removed in vacuo. After addition of Et.sub.2O (150 mL), the reaction mixture was heated to 40? C. and stirred at this temperature for three days. The disappearance of the blue color indicated that the reaction was complete. The precipitated colorless solid was separated off by filtration, washed with Et.sub.2O (3?15 mL) and pentane (3?15 mL), and dried in vacuo. Li(GuaH) was obtained in a yield of about 60%.
[0890] Method B. Guaiazulene (5.00 g, 25.0 mmol, 1.00 eq.) and LiAlH.sub.4 (950 mg, 25.0 mmol, 1.00 eq.) were added to a flask flooded with argon and suspended in THF (150 mL). The reaction mixture was heated to 60? C. and stirred for 24 h at this temperature. The disappearance of the blue color indicated that the reaction was complete. Aluminum hydride was captured by adding 1,4-diazabicyclo[2.2.2]octane (DABCO?). The precipitated solid was separated off by filtration and the solvent was removed in vacuo. Et.sub.2O (150 mL) was added to the residue, and the undissolved colorless-grayish solid was isolated by filtration, washed with Et.sub.2O (3?15 mL) and pentane (3?15 mL), and dried in vacuo. Li(GuaH) was obtained in a yield of about 60%.
[0891] Method C. Guaiazulene (5.00 g, 25.0 mmol, 1.00 eq.), LiH (2.00 g, 250 mmol, ?10 eq.), and LiAlH.sub.4 (48 mg, 1.26 mmol, 0.05 eq., 5 mol %) were placed in a flask flooded with argon and suspended in THF (150 mL). The reaction mixture was heated to 60? C. and stirred at this temperature for 7 days. The disappearance of the blue color indicated that the reaction was complete. Excess lithium hydride was separated off by filtration and the solvent was removed in vacuo. Et.sub.2O (150 mL) was added to the residue, and the undissolved colorless-grayish solid was isolated by filtration, washed with Et.sub.2O (3?15 mL) and pentane (3?15 mL), and dried in vacuo. Li(GuaH) was obtained in a yield of about 60%.
[0892] .sup.1H-NMR (300.1 MHz, [D.sub.6]DMSO): ?.sub.H=5.37 (q, .sup.4J.sub.HH=2.91 Hz, 2H), 5.30 (d, .sup.3J.sub.HH=6.87 Hz, 1H), 4.87 (d, .sup.3J.sub.HH=6.41 Hz, 1H), 2.77 (s, 2H), 2.32 (sept, .sup.3J.sub.HH=6.41 Hz, 1H), 2.01 (s), 1.96 (s), 1.01 (d, .sup.3J.sub.HH=6.85 Hz, 6H) ppm; .sup.13C-NMR (75.5 MHz, [D.sub.6]DMSO): ?.sub.C=136.7 (s, 1C), 135.4 (s, 1C), 121.9 (s, 1C), 118.8 (s, 1C), 115.0 (s, 1C), 108.5 (s, 1C), 106.9 (s, 1C), 106.7 (s, 1C), 100.3 (s, 1C), 36.0 (s, 1C), 29.1 (s, 1C), 24.2 (s, 1C), 22.4 (s, 2C), 13.8 (s, 1C) ppm.
Note:
[0893] The compound Li(GuaH) can also be prepared by reacting guaiazulene with lithium tri-sec-butyl borohydride (L-Selectride? solution, 1.0 M in THF).
[0894] The compounds Na(GuaH) and K(GuaH) can be prepared by reacting guaiazulene with sodium triethylborohydride (e.g., 1.0 M in THF), sodium tri-sec.-butyl borohydride solution (N-Selectride? solution, 1.0 M in THF), potassium triethyl borohydride (e.g., 1.0 M in THF), or potassium tri-sec.-butyl borohydride (K-Selectride? solution, 1.0 M in THF). An isolatable solid was obtained by adding the corresponding crown ether in each case, thus forming Na([15]-crown-5)(GuaH) and K([18]-crown-6)(GuaH). Yellow needles of K([18]-crown-6)(GuaH) suitable for crystal structure analysis were obtained from a saturated THF solution overlaid with pentane at ?20? C.
Example 2: Preparation of Fe(GuaH).SUB.2
[0895] Li(GuaH) (500 mg, 2.42 mmol, 2.0 eq.) and FeCl.sub.2(154 mg, 1.21 mmol, 1.0 eq.) were suspended in diethyl ether (40 mL), and the suspension was stirred at room temperature for 20 h. The solvent was removed in vacuo. The residue was taken up in pentane, and the inorganic salts were separated off by filtration. The remaining red oil was purified by column chromatography (Al.sub.2O.sub.3, CH.sub.2Cl.sub.2). By recrystallization of the isolated product from ethyl acetate or methanol at ?20? C. overnight, the rac diastereomer was obtained as a red solid and isolated by filtration (72%).
[0896] .sup.1H-NMR (300.1 MHz, CDCl.sub.3): ?.sub.H=5.99 (d, .sup.3J.sub.HH=6.52 Hz, 2H), 5.57 (d, .sup.3J.sub.HH=6.57 Hz, 2H), 4.10 (d, .sup.4J.sub.HH=2.39 Hz, 2H), 3.76 (d, .sup.4J.sub.HH=2.56 Hz, 2H) 3.06 (m, 4H), 2.36 (sept., .sup.3J.sub.HH=6.8 Hz, 2H), 2.23 (s, 6H), 1.97 (s, CH.sub.3, 6H), 1.03 (m, 12H) ppm; .sup.13C-NMR (75.5 MHz, CDCl.sub.3): ?.sub.C=145.49 (s, 2C), 136.80 (s, 2C), 123.74 (s, 2C), 120.14 (s, 2C), 85.81 (s, 2C), 81.34 (s, 2C), 81.31 (s, 2C), 71.32 (s, 2C), 66.25 (s, 2C), 36.54 (s, 2C), 27.35 (s, 2C), 23.32 (s, 2C), 21.89 (s, 2C), 21.56 (s, 2C), 11.69 (s, 2C) ppm; HR-MS (El(+)): m/z [FeC.sub.30H.sub.38] detected: 454.1879 [M], calculated: 454.2177; Elemental analysis calculated (%) for C.sub.30H.sub.38Fe (454.48 g/mol): C, 79.28; H, 8.43; detected: C, 79.12, H, 8.32; IR (KBr compact): {tilde over (v)}=2957 (s), 2898 (m), 2866 (m), 1631 (vw), 1593 (w), 1448 (m), 1345 (w), 1310 (w), 1275 (w), 1194 (w), 1181 (w), 1094 (m), 1078 (s), 1042 (w), 1026 (w), 987 (w), 952 (w), 863 (w), 841 (s), 815 (s), 803 (vs), 768 (vs), 694 (m), 590 (s), 551 (m), 538 (s), 511 (vw), 489 (m), 478 (w), 452 (vs), 445 (s), 423 (w) cm.sup.1.
Example 3: Preparation of Ru(GuaH).SUB.2
[0897] Li(GuaH) (500 mg, 2.42 mmol, 2.0 eq.) and Ru(tht).sub.4Cl.sub.2 (636 mg, 1.21 mmol, 1.0 eq.) or Ru(dmso).sub.4Cl.sub.2 (586 mg, 1.21 mmol, 1.0 eq) were suspended in THF (40 mL), and the suspension was stirred at room temperature for 20 h. The solvent was removed in vacuo. The residue was taken up in pentane, and the precipitated inorganic salts were separated off by filtration. The solvent was removed in vacuo, and the raw product that remained was purified by column chromatography (Al.sub.2O.sub.3, CH.sub.2Cl.sub.2). By recrystallization of the isolated product from ethyl acetate or methanol at ?20? C. overnight, the rac diastereomer was obtained as a colorless solid and isolated by filtration (62%).
[0898] .sup.1H-NMR (300.1 MHz, CDCl.sub.3): ?.sub.H=5.94 (d, .sup.3J.sub.HH=5.9 Hz, 2H), 5.61 (d, .sup.3J.sub.HH=5.8 Hz, 2H), 4.49 (d, .sup.4J.sub.HH=2.2 Hz, 2H), 4.31 (d, .sup.4J.sub.HH=2.1 Hz, 2H), 2.92 (d, .sup.2J.sub.HH=14.3 Hz, 2H), 2.83 (d, .sup.2J.sub.HH=14.4 Hz, 2H), 2.39 (sept, .sup.3J.sub.HH=6.7 Hz, 2H), 2.06 (s, 6H), 1.88 (s, 6H), 1.05 (dd, .sup.3J.sub.HH=6.8 Hz, .sup.4J.sub.HH=1.8 Hz, 12H) ppm; .sup.13C-NMR (75.5 MHz, CDCl.sub.3): ?.sub.C=146.52 (s, 2C), 135.82 (s, 2C), 122.95 (s, 2C), 120.33 (s, 2C), 90.47 (s, 2C), 86.15 (s, 2C), 84.29 (s, 2C), 73.82 (s, 2C), 68.14 (s, 2C), 36.50 (s, 2C), 27.23 (s, 2C), 23.24 (s, 2C), 21.94 (s, 2C), 21.64 (s, 2C), 12.06 (s, 2C) ppm; HR-MS (EI(+)): m/z [RuC.sub.30H.sub.38] detected: 500.1545 [M], calculated: 500.1871; Elemental analysis calculated (%) for C.sub.30H.sub.38Ru (499.71 g/mol): C, 72.11; H, 8.08; N, 7.67; detected: C, 71.98, H, 7.59; IR (KBr compact): {tilde over (v)}=2995 (w), 2958 (s), 2895 (m), 2965 (m), 1631 (w), 1598 (w), 1481 (w), 1461 (s), 1447 (s), 1366 (m), 1343 (w), 1310 (w), 1278 (w), 1193 (w), 1180 (w), 1159 (w), 1140 (w), 1107 (w), 1094 (w), 1077 (w), 1043 (m), 1026 (s), 953 (m), 891 (w), 860 (w), 841 (w), 827 (s), 815 (vs), 803 (s), 761 (w), 694 (m), 677 (w), 657 (w), 588 (m), 549 (w), 535 (m), 466 (w), 428 (s), 411 (w) cm.sup.1.
Example 4: Preparation of Ru(Cp*)(GuaH)
[0899] Li(GuaH) (200 mg, 0.97 mmol, 1.0 eq.) and [Ru(Cp*)Cl]4 (264 mg, 0.24 mmol, 0.25 eq.) were stirred in THF (20 mL) for 20 h at room temperature. The solvent was removed in vacuo. The residue was taken up in dichloromethane, and the precipitated inorganic salts were separated off by filtration. The solvent was removed in vacuo, and the raw product that remained was purified by column chromatography (Al.sub.2O.sub.3, CH.sub.2Cl.sub.2). The fraction which caused a yellow band contained the desired product. Ru(Cp*)(GuaH) was isolated as a brown oil after removal of the solvent in vacuo.
[0900] .sup.1H-NMR (300.1 MHz, C.sub.6D.sub.6): ?.sub.H=6.05 (d, J=6.8 Hz, 1H), 5.74 (d, J=6.2 Hz, 1H), 4.21 (d, J=2.3 Hz, 1H), 3.98 (d, J=2.3 Hz, 1H), 2.86 (d, J=4.4 Hz, 1H), 2.38 (m, J=5.6 Hz, 1H), 1.79 (s, 1H), 1.78 (s, 1H), 1.07 (s, 1H), 1.05 (s, 1H) ppm; HR-MS (FD(+)): m/z [RuC.sub.25H.sub.34] detected: 436.1721 [M], calculated: 436.1637.
Example 5: Preparation of [Ru(p-cymene)(GuaH)]PF.SUB.6
[0901] The reactant [Ru(MeCN).sub.2(p-cymene)Cl]PF.sub.6 was prepared according to the following literature specifications: F. B. McCormick, D. D. Cox, W. B. Gleason, Organometallics 1993, 12, 610-612; S. B. Jensen, S. J. Rodger, M. D. Spicer, J. Organomet. Chem. 1998, 556, 151-158; L. Biancalana et al., New J. Chem. 2018, 42, 17574-17586.
[0902] Li(GuaH) (200 mg, 0.97 mmol, 1.0 eq.) and [Ru(MeCN).sub.2(p-cymene)Cl]PF.sub.6 (353 mg, 0.97 mmol, 1.0 eq.), produced from [Ru(p-cymene)RuCl).sub.2].sub.2 were stirred in THF (20 mL) for 20 h at room temperature. The solvent was removed in vacuo, and the residue was taken up in dichloromethane to precipitate the inorganic salts and separate them off by filtration. The solvent was removed and the raw product was taken up in acetonitrile. The concentrated solution was overlaid with diethyl ether and stored at 0? C. overnight. The product precipitated as a colorless solid and was isolated by filtration (69%).
[0903] .sup.1H-NMR (300.1 MHz, DMSO-d.sub.6): ?.sub.H=6.25 (d, .sup.3J.sub.HH=6.1 Hz, 1H), 6.21 (d, .sup.3J.sub.HH=6.2 Hz, 1H), 6.15 (d, .sup.3J.sub.HH=6.1 Hz, 1H), 6.09 (d, .sup.3J.sub.HH=6.1 Hz, 1H), 6.03 (d, .sup.3J.sub.HH=6.0 Hz, 1H), 5.74 (d, .sup.3J.sub.HH=6.0 Hz, 1H), 5.40 (d, .sup.4J.sub.HH=2.3 Hz, 1H), 5.25 (d, .sup.4J.sub.HH=2.2 Hz, 1H), 3.14 (d, .sup.2J.sub.HH=14.4 Hz, 1H), 2.69 (sept, .sup.3J.sub.HH=6.9 Hz, 1H), 2.62 (d, .sup.2J.sub.HH=15.0 Hz, 1H), 2.42 (sept, .sup.3J.sub.HH=6.7 Hz, 1H), 2.14 (s, 1H), 2.05 (s, 1H), 1.21 (d, .sup.3J.sub.HH=4.7 Hz, 3H), 1.19 (d, .sup.3J.sub.HH=4.7 Hz, 6H), 1.02 (t, .sup.3J.sub.HH=6.0 Hz, 6H) ppm; .sup.13C-NMR (75.5 MHz, DMSO-d.sub.6): ?.sub.C=147.35 (s, 1C), 130.53 (s, 1C), 128.96 (s, 1C), 120.96 (s, 1C), 111.30 (s, 1C), 101.19 (s, 1C), 99.83 (s, 1C), 95.49 (s, 1C), 95.20 (s, 1C), 88.08 (s, 1C), 87.79 (s, 1C), 84.98 (s, 1C), 84.87 (s, 1C), 80.62 (s, 1C), 75.24 (s, 1C), 36.07 (s, 1C), 31.49 (s, 1C), 26.04 (s, 1C), 23.58 (s, 1C), 23.20 (s, 1C), 22.77 (s, 1C), 21.87 (s, 1C), 21.68 (s, 1C), 18.06 (s, 1C), 12.21 (s, 1C) ppm; HR-MS (FD(+)): m/z [RuC.sub.25H.sub.33.sup.+] detected: 435.1619 [M], calculated: 435.1553; Elemental analysis calculated (%) for C.sub.25H.sub.33F.sub.6PRu (579.57 g/mol): C, 51.81; H, 5.74; detected: C, 51.72, H, 5.63; IR (KBr compact): {tilde over (v)}=2968 (w), 1478 (w), 1447 (w), 1390 (w), 1059 (vw), 908 (w), 884 (m), 834 (vs), 696 (vw), 679 (vw), 590 (w), 557 (s), 523 (vw), 449 (w), 421 (m) cm.sup.?1.
Example 6: Preparation of Co(GuaH).SUB.2
[0904] A Suspension of Li(GuaH) (500 mg, 2.42 mmol, 2.0 eq.) and COCl.sub.2 (157 mg, 1.21 mmol, 1.0 eq.) were stirred in diethyl ether (40 mL) for 4 h at room temperature. A green-blue solution was obtained. The inorganic salts were separated off by filtration. Co (GuaH).sub.2 was isolated as green-blue oil.
Example 7: Preparation of [Co(GuaH).SUB.2.]PF.SUB.6
[0905] For the synthesis of [Co(GuaH).sub.2]PF.sub.6, a method was developed based on that of Vanicek et al. (Vanicek, S.; Kopacka, H.; Wurst, K.; M?ller, T.; Schottenberger, H.; Bildstein, B., Organometallics 2014, 33, 1152-1156) and Bockman and Kochi (Bockman, T. M.; Kochi, J. K., J. Am. Chem. Soc. 1989, 111, 4669-4683):
[0906] A Suspension of Li(GuaH) (500 mg, 2.42 mmol, 2.0 eq.) and CoCl.sub.2 (157 mg, 1.21 mmol, 1.0 eq.) were stirred in diethyl ether (40 mL) for 4 h at room temperature. A green-blue solution was obtained. The inorganic salts were separated off by filtration. Hot water (50 mL) was added to the filtrate, and the reaction mixture was stirred for 18 h. After separation of a brown solid, a yellow aqueous solution was obtained which contained the product. The brown solid was washed several times with water. The combined aqueous solutions were washed twice with diethyl ether, decolorized with activated carbon. The aqueous solution was concentrated on a rotary evaporator to a minimum of volume (10 mL). An aqueous solution of KPF.sub.6 (334 mg in 20 mL H.sub.2O, 1.81 mmol, 1.5 eq.) was added, and crystallization was facilitated by cooling in an ice bath. The raw yellow product was separated off by filtration, washed thoroughly, once with ice water and twice with diethyl ether, and dried in vacuo. After recrystallization from acetonitrile, overlaid with ethyl acetate, [Co(GuaH).sub.2]PF.sub.6 was separated off by filtration and dried in vacuo (60%).
[0907] .sup.1H-NMR (300.1 MHz, CDCl.sub.3): ?.sub.H=6.47 (d, .sup.3J.sub.HH=6.5 Hz, 2H), 5.77 (d, .sup.3J.sub.HH=6.5 Hz, 2H), 5.45 (br s, 2H), 5.36 (br s, 2H), 3.08 (d, .sup.2J.sub.HH=14.1 Hz, 2H), 2.78 (d, .sup.2J.sub.HH=14.1 Hz, 2H), 2.44 (sept., .sup.3J.sub.HH=6.1 Hz, 2H), 2.24 (s, 6H), 1.96 (s, 6H), 1.06 (m, 12H) ppm; .sup.13C NMR (75.5 MHz, CDCl.sub.3): ?.sub.C=145.37 (s, 2C), 133.08 (s, 2C), 128.36 (s, 2C), 121.31 (s, 2C), 102.63 (s, 2C), 96.96 (s, 2C), 94.78 (s, 2C), 83.27 (s, 2C), 77.81 (s, 2C), 36.55 (s, 2C), 26.05 (s, 2C), 23.16 (s, 2C), 21.70 (s, 2C), 21.43 (s, 2C), 10.64 (s, 2C) ppm; HR-MS (FD(+)): m/z [CoC.sub.30H.sub.38.sup.+] detected: 457.23157, calculated: 457.23055; Elemental analysis calculated (%) for CoC.sub.30H.sub.38PF.sub.6 (602.53 g/mol): C, 59.80; H, 6.36; detected: C, 59.67, H, 6.24; IR (KBr compact): {tilde over (v)}=2964 (w), 1465 (w), 1386 (w), 1363 (w), 1285 (w), 1187 (vw), 1084 (vw), 1043 (vw), 958 (vw), 922 (vw), 876 (m), 832 (vs), 699 (vw), 614 (w), 594 (m), 457 (w), 422 (w) cm.sup.?1.
Note:
[0908] The preparation of [Co(GuaH).sub.2]PF.sub.6 can be carried out in a similar manner starting from isolated Co(GuaH).sub.2.
Example 8: Preparation of Rh(nbd)(GuaH)
[0909] Li(GuaH) (200 mg, 0.97 mmol, 1.0 eq.) and [Rh(nbd)Cl]2 (224 mg, 0.48 mmol, 0.5 eq.) were stirred in THF (20 mL) for 20 h at room temperature. The solvent was removed in vacuo and the residue was taken up in dichloromethane, diethyl ether or pentane to precipitate the inorganic salts and separate them off by filtration. The solvent was removed and the oily product was stored in the refrigerator for a couple of days. Rh(nbd)(GuaH) was then present as a yellow solid (quantitative yield).
[0910] .sup.1H-NMR (300.1 MHz, DMSO-d.sub.6): ?.sub.H=5.80 (d, .sup.3J.sub.HH=6.3 Hz, 1H), 5.60 (d, .sup.3J.sub.HH=6.2 Hz, 1H), 5.29 (d, .sup.4J.sub.HH=2.5 Hz, 1H), 4.83 (d, .sup.4J.sub.HH=2.7 Hz, 1H), 3.32 (m, 2H), 2.91 (m, 6H), 2.39 (sept, .sup.3J.sub.HH=6.1 Hz, 1H), 1.99 (s, 3H), 1.84 (s, 3H), 1.03 (m, 6H), 0.84 (m, 2H) ppm; .sup.13C-NMR (126 MHz, DMSO-d.sub.6): ?.sub.C=146.80 (s, 1C), 144.09 (s, 1C), 132.97 (s, 1C), 129.54 (s, 1C), 121.25 (s, 1C), 119.88 (s, 1C), 112.13 (s, 1C), 103.97 (d, .sup.1J.sub.RhC=4.5 Hz, 1C), 99.92 (d, .sup.1J.sub.RhC=4.1 Hz, 1C), 95.40 (d, .sup.1J.sub.RhC=4.3 Hz, 1C), 85.18 (d, .sup.1J.sub.RhC=4.6 Hz, 1C), 77.36 (d, .sup.1J.sub.RhC=4.6 Hz, 1C), 56.10 (d, .sup.1J.sub.RhC=6.9 Hz, 1C), 46.40 (d, .sup.1J.sub.RhC=2.4 Hz, 1C), 35.75 (s, 1C), 32.40 (d, .sup.1J.sub.RhC=10.3 Hz, 1C), 31.89 (d, .sup.1J.sub.RhC=10.2 Hz, 1C), 26.34 (s, 1C), 23.37 (s, 1C), 21.73 (s, 1C), 21.63 (s, 1C), 11.50 (s, 1C) ppm; HR-MS (FD(+)): m/z [RhC.sub.22H.sub.27] detected: 394.11539 [M], calculated: 394.11678; Elemental analysis calculated (%) for RhC.sub.22H.sub.27 (394.36 g/mol): C, 67.00; H, 6.90; detected: C, 66.87, H, 6.86; IR (KBr compact): {tilde over (v)}=3041 (w), 3027 (w), 2991 (m), 2955 (m), 2923 (s), 2886 (m), 2860 (m), 2842 (m), 1627 (w), 1588 (m), 1456 (m), 1444 (m), 1435 (m), 1407 (w), 1370 (m), 1295 (m), 1276 (w), 1261 (w), 1224 (w), 1196 (w), 1172 (w), 1158 (w), 1101 (w), 1086 (w), 1051 (w), 1044 (w), 1028 (m), 1019 (m), 992 (w), 958 (w), 923 (w), 910 (w), 890 (w), 857 (w), 837 (s), 810 (vs), 792 (s), 779 (s), 764 (m), 757 (m), 691 (w), 660 (w), 619 (w), 587 (w), 556 (w), 531 (w), 507 (w), 494 (w), 472 (w), 440 (w) cm.sup.1.
Example 9: Preparation of Rh(cod)(GuaH)
[0911] Li(GuaH) (200 mg, 0.97 mmol, 1.0 eq.) and [Ru(Cp*)Cl]2 (239 mg, 0.48 mmol, 0.5 eq.) were stirred in THF (20 mL) for 20 h at room temperature. The solvent was removed in vacuo and the residue was taken up in dichloromethane, diethyl ether or pentane to precipitate the inorganic salts and separate them off by filtration. The solvent was removed and the oily product was stored in the refrigerator for a couple of days. Rh(nbd)(GuaH) was then present as a yellow solid (quantitative yield).
[0912] .sup.1H-NMR (300.1 MHz, DMSO-d.sub.6): ?.sub.H=5.99 (d, .sup.3J.sub.HH=5.8 Hz, 1H), 5.77 (d, .sup.3J.sub.HH=6.3 Hz, 1H), 5.08 (d, .sup.4J.sub.HH=2.6 Hz, 1H), 4.70 (d, .sup.4J.sub.HH=2.7 Hz, 1H), 3.69 (m, 2H), 3.63 (m, 2H), 2.85 (d, .sup.2J.sub.HH=14.1 Hz, 1H), 2.71 (d, .sup.2J.sub.HH=14.1 Hz, 1H), 2.34 (sept, .sup.3J.sub.HH=6.7 Hz, 1H), 2.24 (m, 4H), 2.10 (s, 3H), 2.00 (m, 4H), 1.76 (s, 3H), 1.03 (dd, .sup.3J.sub.HH=6.8 Hz, .sup.4J.sub.HH=0.6 Hz, 6H) ppm; .sup.13C-NMR (75.5 MHz, DMSO-d.sub.6): ?.sub.C=143.98 (s, 1C), 132.98 (s, 1C), 122.55 (s, 1C), 120.89 (s, 1C), 106.74 (d, .sup.1J.sub.RhC=3.9 Hz, 1C), 100.76 (d, .sup.1J.sub.RhC=3.2 Hz, 1C), 97.40 (d, .sup.1J.sub.RhC=3.7 Hz, 1C), 87.54 (d, .sup.1J.sub.RhC=4.1 Hz, 1C), 79.86 (d, .sup.1J.sub.RhC=4.2 Hz, 1C), 68.14 (d, .sup.1J.sub.RhC=14.0 Hz, 2C), 67.88 (d, .sup.1J.sub.RhC=14.1 Hz, 2C), 36.83 (s, 1C), 33.15 (s, 2C), 32.73 (s, 2C), 26.56 (s, 1C), 23.56 (s, 1C), 22.07 (s, 1C), 21.99 (s, 1C), 11.41 (s, 1C) ppm; HR-MS (FD(+)): m/z [RhC.sub.23H.sub.31] detected: 410.1484 [M], calculated: 410.1408; Elemental analysis calculated (%) for RhC.sub.23H.sub.31 (410.41 g/mol): C, 67.31; H, 7.61; detected: C, 67.12, H, 7.60; IR (KBr compact): {tilde over (v)}=2996 (w), 2982 (m), 2962 (s), 2952 (s), 2932 (s), 2910 (s), 2889 (s), 2862 (s), 2820 (s), 1587 (m), 1444 (s), 1405 (m), 1380 (m), 1371 (m), 1358 (m), 1320 (m), 1294 (m), 1279 (w), 1261 (w), 1235 (w), 1201 (m), 1179 (m), 1153 (m), 1080 (m), 1045 (m), 1026 (m) 992 (m), 955 (m), 884 (w), 868 (s), 841 (s), 813 (vs), 791 (s), 776 (m), 762 (m), 693 (w), 678 (w), 580 (w), 537 (w), 485 (w), 469 (w), 437 (w) cm.sup.?1.
Example 10: Preparation of [Rh(Cp*)(GuaH)]PF.SUB.6
[0913] Li(GuaH) (200 mg, 0.97 mmol, 1.0 eq.) and [RhCp*Cl.sub.2].sub.2 (300 mg, 0.48 mmol, 0.5 eq.) were stirred in THF (20 mL) for 20 h at room temperature. NH.sub.4PF.sub.6 was then added and the reaction mixture was stirred for a further 2 h. The solvent was removed in vacuo and the residue was taken up in dichloromethan to precipitate and then separate off NH.sub.4Cl by filtration. The solvent of the filtrate was removed in vacuo. The resulting yellow product was obtained in good yield (72%) after washing with pentane and diethyl ether. [Rh(Cp*)(GuaH)]PF.sub.6 was recrystallized from a concentrated solution in dichloromethane, overlaid with pentane, and obtained in the form of yellow crystalline blocks. These were separated off by filtration and dried in vacuo.
[0914] .sup.1H-NMR (300.1 MHz, DMSO-d.sub.6): ?.sub.H=6.34 (d, .sup.3J.sub.HH=6.3 Hz, 1H), 5.76 (d, .sup.3J.sub.HH=6.2 Hz, 1H), 5.68 (d, .sup.4J.sub.HH=2.4 Hz, 1H), 5.46 (d, .sup.4J.sub.HH=2.0 Hz, 1H), 3.17 (d, .sup.2J.sub.HH=14.4 Hz, 1H), 2.44 (sept, .sup.3J.sub.HH=7.0 Hz, 1H), 2.40 (d, .sup.2J.sub.HH=13.8 Hz, 2H), 2.03 (s, 3H), 1.97 (s, 3H), 1.94 (s, 15H), 1.03 (t, .sup.3J.sub.HH=6.7 Hz, 6H) ppm; .sup.13C-NMR (75.5 MHz, DMSO-d.sub.6): ?.sub.C=145.71 (s, 1C), 129.49 (s, 1C), 127.89 (s, 1C), 120.35 (s, 1C), 105.62 (d, .sup.1J.sub.RhC=7.0 Hz, 1C), 99.63 (d, .sup.1J.sub.RhC=7.8 Hz, 5C), 98.77 (d, .sup.1J.sub.RhC=6.9 Hz, 1C), 96.07 (d, .sup.1J.sub.RhC=6.5 Hz, 1C), 88.10 (d, .sup.1J.sub.RhC=7.5 Hz, 1C), 81.81 (d, .sup.1J.sub.RhC=7.6 Hz, 1C), 35.59 (s, 1C), 24.08 (s, 1C), 21.36 (s, 1C), 21.19 (s, 1C), 21.10 (s, 1C), 9.49 (s, 1C), 8.99 (s, 5C), ppm; HR-MS (FD(+)): m/z [RhC.sub.25H.sub.34] detected: 437.17261 [M], calculated: 437.17155; Elemental analysis calculated (%) for RhC.sub.25H.sub.34PF.sub.6 (582.42 g/mol): C, 51.56; H, 5.88; detected: C, 51.52, H, 5.84;
[0915] IR (KBr compact): {tilde over (v)}=2960 (w), 1464 (w), 1385 (w), 1031 (vw), 874 (w), 836 (vs), 764 (w), 739 (w), 699 (w), 611 (w), 591 (w), 557 (s), 506 (w), 492 (w), 462 (w), 438 (w) cm.sup.?1.
Example 11: Preparation of PtMe.SUB.3.(GuaH)
[0916] Li(GuaH) (500 mg, 2.42 mmol, 1.0 eq,) and [PtMe.sub.3I]4 (890 mg, 0.61 mmol, 0.25 eq,) were suspended in diethyl ether (40 mL), and the suspension was stirred at 40? C. for 30 min, then at room temperature for 4 h. A yellow solution was obtained. The solvent was removed in vacuo. It is very important to remove the solvent completely, because otherwise lithium iodide remains in solution and contamination of the product cannot be ruled out. The oily residue is taken up in pentane (40 mL), and inorganic salts and any unreacted reactants are separated off by filtration. The solvent of the filtrate is removed in vacuo, and PtMe.sub.3(GuaH) is obtained as a yellow oil in good yield (82%). Further purification of the product can be carried out by means of column chromatography (silica, hexane).
[0917] .sup.1H-NMR (300.1 MHz, DMSO-d.sub.6): ?.sub.H=6.00 (d, .sup.3J.sub.HH=6.3 Hz, 1H), 5.73 (d, .sup.4J.sub.HH=2.8 Hz, 1H), 5.56 (d, .sup.3J=6.2 Hz, 1H,), 5.38 (d, .sup.3J=3.0 Hz, 1H), 2.98 (d, .sup.2J.sub.HH=14.3 Hz, 1H), 2.53 (d, 1H, .sup.2J.sub.HH=14.3 Hz, 1H), 2.40 (sept, .sup.3J.sub.HH=6.8 Hz, 1H), 1.94 (s, 3H), 1.90 (s, 3H), 1.03 (d, .sup.3J.sub.HH=6.8 Hz, 3H), 1.01 (d, .sup.3J.sub.HH=6.8 Hz, 3H), 0.66 (s, J.sub.195Pt-1H=80.8 Hz, 9H, PtMe.sub.3) ppm; .sup.13C-NMR (75.5 MHz, DMSO-d.sub.6): ?.sub.C=144.79 (s, 1C), 130.01 (s, 1C), 123.75 (s, 1C), 119.74 (s, 1C), 110.77 (s, 1C), 106.83 (s, 1C), 106.18 (s, 1C), 91.60 (s, 1C), 90.04 (s, 1C), 35.81 (s, 1C), 24.10 (s, 1C), 22.06 (s, 1C), 21.56 (s, 1C), 21.26 (s, 1C), 9.54 (s, 1C), ?14.76 (PtMe.sub.3); HR-MS (FD(+)): m/z [PtC.sub.18H.sub.28] detected: 439.18065 [M], calculated: 439.18387; IR (KBr compact): {tilde over (v)}=2957 (vs), 2891 (vs), 2809 (m), 1634 (vw), 1598 (w), 1461 (m), 1431 (m), 1376 (m), 1359 (s), 1314 (s), 1285 (m), 1251 (w), 1210 (w), 1192 (s), 1095 (w), 1081 (w), 1028 (s), 998 (s), 955 (s), 886 (vs), 839 (m), 812 (w), 786 (w), 759 (w), 693 (w), 673 (w), 653 (w), 583 (w), 555 (s), 533 (m), 504 (w), 469 (w), 425 (m) cm.sup.?1.
Example 12: Preparation of [Pt(cod)(GuaH)]PF.SUB.6
[0918] Li(GuaH) (200 mg, 0.97 mmol, 1.0 eq.) and [Pt(cod)Cl.sub.2] (363 mg, 0.97 mmol, 1.0 eq.) were stirred in THF (20 mL) for 24 h at room temperature. The reaction mixture changed color to orange during the reaction time. NH.sub.4PF.sub.6 was added. After further stirring for 2 h, the solvent was removed in vacuo, acetonitrile (20 mL) was added, and NH.sub.4Cl was separated off by filtration. The solvent of the filtrate was removed in vacuo. [Pt(cod)(GuaH)]PF.sub.6 was obtained as an orange solid in good yield (78%). [Pt(cod)(GuaH)]PF.sub.6 can be recrystallized at ?20? C. from THF overlaid with pentane.
[0919] .sup.1H NMR (300.1 MHz, DMSO-d.sub.6): ?.sub.H=6.31 (d, .sup.3J.sub.HH=6.3 Hz, 1H), 6.30-6.14 (m, 2H), 5.83 (d, .sup.3J.sub.HH=6.4 Hz, 1H), 5.28-4.95 (m, 4H), 3.24 (d, .sup.2J.sub.HH=14.6 Hz, 1H), 2.78 (d, .sup.2J.sub.HH=14.6 Hz, 1H), 2.42 (m, 7H), 2.18 (s, 3H), 2.11 (s, 3H), 1.09 (d, .sup.4J.sub.HH=0.9 Hz, 3H), 1.07 (d, .sup.4J.sub.HH=0.9 Hz, 3H) ppm; .sup.13C-NMR (75.5 MHz, DMSO-d.sub.6): ?.sub.C=146.36 (s, 1C), 128.54 (s, 1C), 127.40 (s, 1C), 120.63 (s, 1C), 115.07 (s, 1C), 111.05 (s, 1C), 109.92 (s, 1C), 93.42 (s, 1C), 87.76 (s, 1C), 82.72 (s, 2C), 81.73 (s, 2C), 35.72 (s, 1C), 31.90 (s, 1C), 31.56 (s, 2C), 24.92 (s, 1C), 22.19 (s, 1C), 21.39 (s, 1C), 21.37 (s, 1C), 10.14 (s, 1C) ppm; HR-MS (FD(+)): m/z [PtC.sub.23H.sub.31] detected: 501.20506 [M], calculated: 501.20524; Elemental analysis calculated (%) for PtC.sub.23H.sub.31PF.sub.6 (647.55 5 g/mol): C, 42.66; H, 4.83; detected: C, 42.55, H, 4.78; IR (KBr compact): {tilde over (v)}=2964 (w), 1435 (w), 1386 (w), 1363 (w), 1285 (w), 1032 (vw), 874 (w), 826 (vs), 697 (w), 556 (s), 471 (vw) cm.sup.?1.
Example 13: Preparation of Cu(PPh.SUB.3.)(GuaH)
[0920] Li(GuaH) (200 mg, 0.97 mmol, 1.0 eq,) and [Cu(PPh.sub.3)Cl]4 (350 mg, 0.24 mmol, 0.25 eq,) were stirred in THF at ?78? C. for about 3 h. The reaction mixture was slowly warmed to room temperature overnight while stirring. In the process, it changed color to green-yellow. The solvent was removed in vacuo, and diethyl ether was added to precipitate and separate off inorganic salts by filtration. The solvent of the filtrate was removed in vacuo. The residue was washed with pentane, and Cu(PPh.sub.3)(GuaH) pale yellow solid was obtained in near quantitative yield.
[0921] .sup.1H NMR (300.1 MHz, C.sub.6D.sub.6): ?.sub.H=7.35 (m, 6H), 6.99 (m, 9H), 6.22 (d, .sup.3J.sub.HH=3.0 Hz, 1H), 6.17 (d, .sup.3J.sub.HH=3.0 Hz, 1H), 6.06 (dd, .sup.3J.sub.HH=6.3 Hz, .sup.4J.sub.HH=2.4 Hz, 1H), 5.85 (d, .sup.3J.sub.HH=6.2 Hz, 1H), 3.33 (d, .sup.2J.sub.HH=15.1 Hz, 1H), 3.23 (d, .sup.2J.sub.HH=15.1 Hz, 1H), 2.45 (s, 3H), 2.38 (s, 3H), 2.33 (sept, .sup.3J.sub.HH=6.8 Hz, 1H), 0.95 (d, .sup.3J.sub.HH=6.8 Hz, 3H), 0.90 (d, .sup.3J.sub.HH=6.8 Hz, 3H) ppm; .sup.13C-NMR (75.5 MHz, C.sub.6D.sub.6): ?.sub.C=145.04 (s, 1C), 135.27 (s, 3C), 134.07 (d, .sup.2J.sub.PC=15.8 Hz, 6C), 133.37 (d, .sup.1J.sub.PC=43.5 Hz, 3C), 130.35 (s, 1C), 128.76 (d, 3J.sub.PC=10.4 Hz, 6C), 120.94 (s, 1C), 118.50 (s, 1C), 116.14 (s, 1C), 115.42 (s, 1C), 103.64 (s, 1C), 94.73 (s, 1C), 89.24 (s, 1C), 37.11 (s, 1C), 28.17 (s, 1C), 24.43 (s, 1C), 22.32 (s, 1C), 22.11 (s, 1C), 13.19 (s, 1C) ppm; HR-MS (FD(+)): m/z [C.sub.33H.sub.34CuP] detected: 524.17053 [M], calculated: 524.16941; Elemental analysis calculated (%) for C.sub.33H.sub.34CuP (525.15 g/mol): C, 75.48; H, 6.53; detected: C, 75.34, H, 6.49; IR (KBr compact): {tilde over (v)}=2963 (m), 2871 (w), 1632 (w), 1593 (w), 1464 (m), 1435 (m), 1385 (m), 1362 (m), 1315 (w), 1284 (w), 1246 (w), 1199 (w), 1186 (w), 1083 (w), 1043 (w), 1029 (w), 996 (w), 958 (w), 872 (m), 798 (vs), 696 (m), 592 (w), 548 (m), 499 (w), 455 (w), 420 (w) cm.sup.?1.
Example 14: Preparation of Zn(Mes)(GuaH)
[0922] Li(GuaH) (200 mg, 0.97 mmol, 1.0 eq,) and ZnCl.sub.2 (66 mg, 0.48 mmol, 0.5 eq,) were suspended in THF (20 mL) and stirred at room temperature for 24 h. A yellow solution was obtained. The inorganic salts were separated off by filtration. ZnMes.sub.2 (146 mg, 0.48 mmol, 0.5 eq,) was added to the filtrate, which contained the desired zinconcene-type intermediate Zn(GuaH).sub.2. The reaction mixture was stirred for 3 h before the solvent was removed in vacuo. The residue was taken up in pentane, and the solution was stored overnight at ?80? C. to precipitate any unreacted Zn(GuaH).sub.2 and ZnMes.sub.2. After filtration through a syringe filter, the solvent of the filtrate was removed in vacuo. Zn(Mes)(GuaH) was obtained as yellow-orange oil in good yield (80%).
[0923] .sup.1H-NMR (300.1 MHz, C.sub.6D.sub.6): ?.sub.H=6.78 (s, 1H), 6.02 (q, .sup.4J.sub.HH=2.4 Hz, 1H), 6.00 (d, .sup.4J.sub.HH=3.1 Hz, 1H), 5.97 (d, .sup.4J.sub.HH=3.0 Hz, 1H), 5.71 (d, .sup.3J.sub.HH=6.2 Hz, 1H), 3.12 (d, .sup.2J.sub.HH=14.0 Hz, 1H), 2.86 (d, .sup.2J.sub.HH=14.0 Hz, 1H), 2.27 (sept, .sup.3J.sub.HH=6.8 Hz, 1H), 2.20 (s, 3H), 2.17 (s, 3H), 2.16 (s, 6H), 0.91 (t, .sup.3J.sub.HH=6.4 Hz, 6H) ppm; .sup.13C-NMR (75.5 MHz, C.sub.6D.sub.6): ?.sub.C=147.11 (s, 1C), 145.64 (s, 1C), 140.55 (s, 1C), 137.27 (s, 2C), 133.54 (s, 1C), 126.18 (s, 2C), 122.72 (s, 1C), 122.07 (s, 1C), 120.94 (s, 1C), 119.82 (s, 1C), 110.58 (s, 1C), 101.31 (s, 1C), 93.76 (s, 1C), 36.98 (s, 1C), 28.42 (s, 1C), 27.01 (s, 2C), 23.88 (s, 1C), 22.05 (s, 1C), 22.03 (s, 1C), 21.25 (s, 1C), 12.18 (s, 1C) ppm; HR-MS (FD(+)): m/z [C.sub.24H.sub.30Zn] detected: 382.16545 [M], calculated: 382.16390; IR (KBr compact): {tilde over (v)}=2957 (s), 2914 (s), 2865 (m), 2724 (w), 1631 (w), 1594 (w), 1553 (w), 1443 (s), 1373 (m), 1359 (w), 1335 (w), 1313 (w), 1288 (w), 1236 (w), 1193 (w), 1081 (s), 953 (m), 844 (s), 815 (s), 771 (s), 756 (vs), 702 (m), 659 (w), 619 (w), 584 (w), 564 (w), 537 (m), 484 (w), 468 (w), 418 (w).
Example 15: Photohydrosilylation of 1-Octene with Pentamethylsiloxane Using PtMe.SUB.3 .(GuaH) as Catalyst
[0924] To a solution of PtMe.sub.3(GuaH) (cf. Example 11) in cyclohexane (25 mL; 10 ppm=2.5?10.sup.?5 mol/L) were added 661 mg of pentamethylsiloxane (4.45 mmol) and 500 mg 1-octene (4.45 mmol). The solution was irradiated with UV light with stirring for 30 min, and then stirred for a further 18 h. The raw product was purified by column chromatography (hexane). According to .sup.1H NMR spectrum, the isolated product had no impurities.
[0925] Yield according to .sup.1H NMR spectrum (before purification): quantitative; isolated yield about 80%.
NMR experiments with 5 ppm Pt:
Stock Solution (1.78 M):
[0926] 500 mg 1-octene (4.45 mmol), 661 mg pentamethylsiloxane (4.45 mmol), 2.5 mL C.sub.6D.sub.6
[0927] Pt complex solution (0.0889 mM=0.0005 mol % compared to stock solution):
[0928] 0.391 mg PtMe.sub.3(GuaH), 5 mL C.sub.6D.sub.6
[0929] 0.25 mL stock solution and 0.25 mL Pt complex solution were filled into an NMR tube. The tube was shaken and then irradiated with UV light (Osram Ultra Vitalux, 300 W, 220 V, plant lamp) for 5 min. .sup.1H NMR spectra were recorded at time 0 h and after about 0.25 h, 0.50 h, 1 h, 2 h, 4 h, 8 h, 24 h and 48 h.
[0930] The invention is not limited to one of the embodiments described above but may be modified in many ways.
[0931] It can be seen that the invention relates to a method for preparing compounds of the general formula M.sup.AY.sub.n(AzuH) (I), where M.sup.A=alkali metal, Y=neutral ligand, n=0, 1, 2, 3, or 4 and AzuH is azulene (bicyclo[5.3.0]decapentaene) or an azulene derivative that bears a hydride anion H.sup.? in the 4, 6 or 8 position in addition to an H atom. The invention additionally provides compounds obtainable by this method, and a method using such compounds for preparation of complexes of metals of groups 6 to 12. The invention further relates to complexes of middle transition metals (groups 6, 7 and 8) and later transition metals (groups 9, 10, 11 and 12) which each have at least one H-dihydroazulenyl anion (AzuH).sup.1?, and to the use of all the aforementioned transition metal complexes as precatalysts or catalysts or electron transfer reagents in a chemical reaction or as precursor compounds for production of a layer containing a metal M, or of a metal layer consisting of the metal M, especially on at least one surface of a substrate. The invention also provides a substrate obtainable by such a method, i.e., using a metal complex according to one of the formulae M(L.sub.K).sub.f(AzuH).sub.m (III), M(L.sub.N)(AzuH).sub.q(IV), [M(L.sub.S).sub.g(AzuH).sub.v]X (V) and [M(L.sub.T)(AzuH).sub.z]X (VI).
[0932] The method described allows defined alkali metal H-dihydroazulenyl compounds of the type M.sup.AY.sub.n(AzuH) (I) to be prepared in a simple, cost-effective and reproducible manner in high purity and good yield. The method can also be carried out on an industrial scale. After their isolation, without complex purification, the compounds usually do not have any NMR spectroscopically detectable impurities. Owing to their high purity, they are suitable as reactants for the preparation of transition metal complexes, in particular of metals of group 6, group 7, group 8, group 9, group 10, group 11, and group 12. The method described herein allows such metal complexes of middle and late transition metals to be obtained in a simple, reproducible and comparatively cost-effective manner, and in good (isomeric) purity and good to very good yields. They are a relatively cost-effective and, and in some cases, particularly sustainable alternative to metal complexes containing cyclopentadienyl ligands. This applies in particular to use as precatalysts, catalysts and electron transfer reagents in chemical reactions. Furthermore, they are particularly suitable as precursor compounds for preparing high-quality substrates which have at least one metal-containing layer or at least one metal layer on at least one surface. The metal or the metals are in this case selected from group 6, group 7, group 8, group 9, group 10, group 11, and group 12.
[0933] All features and advantages resulting from the claims, the description and the figures, including constructive details, spatial arrangements and method steps, can be essential to the invention, both in themselves and in the most diverse combinations.