1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO) (P.SUP.i.Pr.SUB.3.).SUB.2 .moieties with 8-mercaptoquinolato co-ligand as an organic catalyst

Abstract

A 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with 8-mercaptoquinolato co-ligand, its synthesis, and its use as a catalyst in organic processes.

Claims

1. A 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with an 8-mercaptoquinolato co-ligand having the formula I: ##STR00005##

2. The 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with the 8-mercaptoquinolato co-ligand of claim 1, wherein the compound is obtained as a yellow solid.

3. A method of making the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with the 8-mercaptoquinolato co-ligand of claim 1, the method comprising: stirring 8-mercaptoquinoline and K.sub.2CO.sub.3 in a solvent of CH.sub.2Cl.sub.2 and MeOH to obtain a first reaction mixture; adding the first reaction mixture to a solution of a complex [{Ru(CO)Cl(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] in CH.sub.2Cl.sub.2 to obtain a second reaction mixture; stirring the second reaction mixture for at least about 1 hour to obtain a precipitate; removing the solvent under reduced pressure to retrieve the precipitate; washing the precipitate; drying the precipitate; and obtaining the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with the 8-mercaptoquinolato co-ligand.

4. The method of making the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with the 8-mercaptoquinolato co-ligand of claim 3, wherein the precipitate is yellow.

5. The method of making the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with the 8-mercaptoquinolato co-ligand of claim 3, wherein the precipitate is washed with n-hexane and MeOH.

6. The method of making the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with the 8-mercaptoquinolato co-ligand of claim 3, wherein washing the precipitate removes unreacted starting materials and formed KCl.

7. The method of making the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with the 8-mercaptoquinolato co-ligand of claim 3, wherein the precipitate is dried in a vacuum.

8. The method of making the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with the 8-mercaptoquinolato co-ligand of claim 3, wherein the 8-mercaptoquinoline and K.sub.2CO.sub.3 are added in equimolar amounts.

9. The method of making the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with 8-mercaptoquinolato co-ligand of claim 3, wherein the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with the 8-mercaptoquinolato co-ligand is obtained as a yellow solid.

10. The method of making the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(P.sup.iPr.sub.3).sub.2 moieties with 8-mercaptoquinolato co-ligand of claim 3, wherein the 1,4-divinylphenylene-bridged diruthenium complex bearing two RU(CO)(P.sup.iPr.sub.3).sub.2 moieties with the 8-mercaptoquinolato co-ligand is obtained in an about 89% yield.

Description

BRIEF DESCRIPTION OF THE DRAWINGS

(1) FIG. 1 shows .sup.1H-NMR analysis spectrum of complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)]

(2) FIG. 2 shows .sup.31P-NMR analysis (162 MHz, CD.sub.2Cl.sub.2) of complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)].

(3) FIG. 3 shows Cyclic (upper) and square-wave (lower) voltammograms of complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] vs. Cp.sub.2Fe.sup.0/+ in CH.sub.2Cl2/n-NBu.sub.4PF.sub.6 at a scan rate =0.1 V.sup.s-1 or at step potential of 4 mV and a frequency of 15 Hz.

(4) FIGS. 4A and 4B IR spectroscopic changes upon the first (left) and the second oxidation (right) of the complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] in CH.sub.2Cl.sub.2/NBu.sub.4PF.sub.6.

(5) FIGS. 5A and 5B show UV/Vis/NIR spectroscopic changes during the first and the second oxidation of the 1,4-divinylphenylene-bridged diruthenium complex bearing two RU(CO)(P.sup.iPr.sub.3).sub.2 moieties with 8-mercaptoquinolato co-ligand in CH.sub.2Cl.sub.2/NBu.sub.4PF.sub.6.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

(6) The following definitions are provided for the purpose of understanding the present subject matter and for construing the appended patent claims.

Definitions

(7) Throughout the application, where compositions are described as having, including, or comprising specific components, or where processes are described as having, including, or comprising specific process steps, it is contemplated that compositions of the present teachings can also consist essentially of, or consist of, the recited components, and that the processes of the present teachings can also consist essentially of, or consist of, the recited process steps.

(8) It is noted that, as used in this specification and the appended claims, the singular forms a, an, and the include plural references unless the context clearly dictates otherwise.

(9) In the application, where an element or component is said to be included in and/or selected from a list of recited elements or components, it should be understood that the element or component can be any one of the recited elements or components, or the element or component can be selected from a group consisting of two or more of the recited elements or components. Further, it should be understood that elements and/or features of a composition or a method described herein can be combined in a variety of ways without departing from the spirit and scope of the present teachings, whether explicit or implicit herein.

(10) The use of the terms include, includes, including, have, has, or having should be generally understood as open-ended and non-limiting unless specifically stated otherwise.

(11) The use of the singular herein includes the plural (and vice versa) unless specifically stated otherwise. In addition, where the use of the term about is before a quantitative value, the present teachings also include the specific quantitative value itself, unless specifically stated otherwise. As used herein, the term about refers to a 10% variation from the nominal value unless otherwise indicated or inferred.

(12) The term optional or optionally means that the subsequently described event or circumstance may or may not occur, and that the description includes instances where said event or circumstance occurs and instances in which it does not.

(13) It will be understood by those skilled in the art with respect to any chemical group containing one or more substituents that such groups are not intended to introduce any substitution or substitution patterns that are sterically impractical and/or physically non-feasible.

(14) Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood to one of ordinary skill in the art to which the presently described subject matter pertains.

(15) Where a range of values is provided, for example, concentration ranges, percentage ranges, or ratio ranges, it is understood that each intervening value, to the tenth of the unit of the lower limit, unless the context clearly dictates otherwise, between the upper and lower limit of that range and any other stated or intervening value in that stated range, is encompassed within the described subject matter. The upper and lower limits of these smaller ranges may independently be included in the smaller ranges, and such embodiments are also encompassed within the described subject matter, subject to any specifically excluded limit in the stated range. Where the stated range includes one or both of the limits, ranges excluding either or both of those included limits are also included in the described subject matter.

(16) Throughout the application, descriptions of various embodiments use comprising language. However, it will be understood by one of skill in the art, that in some specific instances, an embodiment can alternatively be described using the language consisting essentially of or consisting of.

(17) For purposes of better understanding the present teachings and in no way limiting the scope of the teachings, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and claims, are to be understood as being modified in all instances by the term about. Accordingly, unless indicated to the contrary, the numerical parameters set forth in the following specification and attached claims are approximations that may vary depending upon the desired properties sought to be obtained. At the very least, each numerical parameter should at least be construed in light of the number of reported significant digits and by applying ordinary rounding techniques.

(18) The present subject matter relates to a novel 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2 moieties with the general formula [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)].

(19) This six-coordinated, octahedral, 18-VEs type-complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] has been successfully prepared in high yields by substitution of the chloro ligands of the precursor complex [{Ru(CO)Cl(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] with the corresponding deprotonated 8-mercaptoquinoline in a CH.sub.2Cl.sub.2/MeOH solvent mixture. The complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] was routinely characterized in the neutral state by classical IR, UV/Vis and NMR spectroscopy techniques, and in its two different reachable oxidized states by IR, UV/Vis/NIR spectroelectrochemistry along with electrochemical techniques. The 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2 moieties may function as a catalyst in organic processes.

(20) The product can be acquired in exceptional yields (average about 89%) by substitution of the chloro ligands of the precursor complex [{Ru(CO)Cl(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] with the corresponding deprotonated 8-mercaptoquinoline in a CH.sub.2Cl.sub.2/MeOH solvent mixture. The reaction components could be purified by some non-chromatographic techniques. The product can be analyzed using spectral data; IR, NMR & elemental analysis. The prepared compound can be used as a catalyst for organic processes.

(21) In an embodiment, the present subject matter relates to a 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2 moieties having the formula I:

(22) ##STR00002##

(23) In certain embodiments, the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2 moieties can be obtained as a yellow solid.

(24) In another embodiment, the present subject matter relates to a catalyst for organic reactions and processes.

(25) In one more embodiment, the present subject matter relates to a method of making the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2 moieties, the method comprising: stirring 8-mercaptoquinoline and K.sub.2CO.sub.3 in a solvent of CH.sub.2Cl.sub.2 and MeOH to obtain a first reaction mixture; adding the first reaction mixture to a solution of a complex [{Ru(CO)Cl(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] in CH.sub.2Cl.sub.2 to obtain a second reaction mixture; stirring the second reaction mixture for at least about 1 hour to obtain a precipitate; removing the solvent under reduced pressure to retrieve the precipitate; washing the precipitate; drying the precipitate; and obtaining the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2 moieties.

(26) The present production methods can be further seen by referring to the following Scheme 1:

(27) ##STR00003##

(28) In an embodiment of the present production methods, the precipitate can be yellow.

(29) In another embodiment of the present production methods, the precipitate can be washed with n-hexane and MeOH.

(30) In a further embodiment of the present production methods, the precipitate can be dried in a vacuum.

(31) In another embodiment of the present production methods, washing the precipitate may remove unreacted starting materials and formed KCl.

(32) In a further embodiment of the present production methods, the 8-mercaptoquinoline and K.sub.2CO.sub.3 may be added in equimolar amounts.

(33) In another embodiment of the present production methods, the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2 moieties can be obtained as a yellow solid.

(34) In an additional embodiment of the present production methods, the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2 moieties can be obtained in an about 89% yield.

(35) The following examples relate to various methods of manufacturing the specific compounds and application of the same, as described herein. All compound numbers expressed herein are with reference to the synthetic pathway figures shown above.

EXAMPLES

Example 1

(36) Preparation of 1,4-Divinylphenylene-Bridged Diruthenium Complex Bearing Two Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2 moieties

(37) 0.8 mmol of 8-mercaptoquinoline and equimolar amounts of K.sub.2CO.sub.3 (111 mg, 0.8 mmol, 2.2 eq.) were stirred at room temperature in a solvent mixture of 10 mL of CH.sub.2Cl.sub.2 and 10 mL of MeOH for 30 min. This solution was slowly added via cannula to a solution of 395 mg (0.36 mmol, 1 eq.) of the complex [{Ru(CO)Cl(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] in 10 mL of CH.sub.2Cl.sub.2. After complete addition, stirring was continued for one further hour at room temperature to give a deep yellow solution. The solvents were removed under reduced pressure and the yellow precipitate was washed twice with 15 mL of n-hexane and 15 mL of MeOH each to remove unreacted starting material and the formed KCl. The resulting residue was then dried in vacuum. 0.8 mmol, 2.2 eq. of 8-mercaptoquinoline yielded 425 mg (0.32 mmol, 89%) of complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)].

(38) Characterization of the prepared compound was determined using .sup.1H NMR and .sup.31P-NMR as shown in FIGS. 1 and 2, respectively. The elemental analysis can be seen as follows.

(39) Elemental analysis calculated for C.sub.66H.sub.104N.sub.2O.sub.2S.sub.2P.sub.4Ru.sub.2: C: 58.82; H: 7.78; N: 2.08; S: 4.76. Found C: 59.35%; H: 7.95%; N: 2.07%; S: 4.69. IR (ATR, in cm.sup.1): 2950, 2930(CH aryl, vinyl), 1880 Ru(CO), 1585 (CN), 1560, 1500 (CC vinyl, aryl). UV/Vis (.sub.max (nm), (M.sup.1.Math.cm.sup.1)): 355 (1.710.sup.4; 450, 1.610.sup.4).

(40) .sup.1H NMR (400 MHz, CD.sub.2Cl.sub.2) as depicted in FIG. 1: : 8.92 (d, 2H, .sup.3J.sub.H-H=17.0 Hz, H(1)), 8.78 (dd, 2H, .sup.3J.sub.H-H=4.7 Hz, .sup.4J.sub.H-H=0.4 Hz, H.sub.(12)), 7.89(d, 2H, .sup.3J.sub.H-H=8.3 Hz, H.sub.(10)), 7.28 (vt, 2H, .sup.3J.sub.H-H=7.9 Hz, H.sub.(7)), 7.15 (dd, 2H, .sup.3J.sub.H-H=8.3 Hz, .sup.3J.sub.H-H=4.7 Hz, H.sub.(11)), 7.05 (s, 4H, H.sub.(4)), 6.75 (d, 2H, .sup.3J.sub.H-H=7.9 Hz, H.sub.(6)), 6.65 (d, 2H, .sup.3J.sub.H-H=7.7 Hz, H.sub.(8)), 6.55 (dt, 2H, .sup.3J.sub.H-H=17.0 Hz, .sup.4J.sub.H-P=2.0 Hz, H.sub.(2)), 2.15-2.10 (m, 12H, PCHCH.sub.3), 1.15-0.95(m, 72H, PCHCH.sub.3) ppm.

(41) .sup.31P-NMR (162 MHz, CD.sub.2Cl.sub.2) as depicted in FIG. 2: : 30.21 (s, PiPr3) ppm. .sup.13C{H1}-NMR (101 MHz, CD.sub.2Cl.sub.2): 209.2 (t, .sup.2J.sub.C-P=13.8 Hz, C.sub.(14)), 179.1 (t, .sup.2J.sub.C-P=13.6 Hz, C.sub.(1)), 170.4 (s, C.sub.(5)), 156.5 (s, C.sub.(13)), 148.2 (s, C.sub.(10), 146.3 (s, C.sub.(3)), 136.2 (t, .sup.3J.sub.C-P=1.8 Hz, C.sub.(12)), 132.8 (t, .sup.3J.sub.C-P=3.1 Hz, C.sub.(2)), 131.2 (s, C.sub.(9)), 130.2 (s, C.sub.(7)), 124.8 (s, C.sub.(4)), 121.5 (s, C.sub.(11)), 114.3 (s, C.sub.(6)), 108.4 (s, C.sub.(8)), 24.5 (t, .sup.2J.sub.C-P=8.8 Hz, CH(CH.sub.3).sub.2), 19.5 and 19.2 (s, (CH.sub.3).sub.2CH) ppm.

(42) ##STR00004##

Example 2

NMR Characterization

(43) NMR Characterization

(44) To investigate the electrochemical electronic coupling, polyelectrochroic behavior, catalytic activity and spectro(electro)scopic features of bis(ruthenium-alkenyl) moieties incorporated into 1,4-divinylphenylene-bridge linker terminated with deprotonated, 8-mercaptoquinolato as monoanionic, chelating, bidentate co-ligands. We have successfully prepared a novel [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] as depicted in Scheme 1 previously illustrated.

(45) This six-coordinated, octahedaral, bis(ruthenium-alkenyl) type-complex [dRu2NS] was classically prepared by in high yields by substitution of the chloro ligands of the precursor complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] with the corresponding deprotonated 8-mercaptoquinoline in a CH.sub.2Cl.sub.2/MeOH solvent mixture according to a routine protocol in a stoichiometric ratio of 1:2. Upon addition of the solution of the deprotonated chelate 2-mercaptoquinoline, the reaction solution color changed promptly from red to deep yellow with the concomitant precipitation of KCl. [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] was routinely characterized in their neutral state by conventional IR, UV/Vis and NMR spectroscopy and analytical techniques, and in its two different reachable oxidized states by IR, UV/Vis/NIR spectroelectrochemistry.

(46) .sup.31P-NMR spectrum of the complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)], likewise other ruthenium-alkenyl of similar family, showed a sharp singlet resonance at =30.2 ppm, confirming that the four P.sup.iPr.sub.3 ligands are chemically equivalent in which two of them are trans-disposed at each {Ru} end-groups. .sup.1H-NMR spectrum shows classical doublet at 8.92 ppm and doublet of triplet at 6.55 ppm of the four equivalent vinylic protons RuCH(H.sub.1) and RuCHCH (H.sub.2) with a large coupling constant .sup.3J.sub.H-H of about 13.1 Hz, respectively. This high coupling constant confirms a trans-geometry at the two vinylic double bonds. .sup.13C-NMR spectrum of complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] shows classical olefinic signals of the two equivalent - and -vinylic carbons with two triplets at 179.1 ppm for RuC (C.sub.1) and at 132.8 ppm for RuCC (C.sub.2) with a .sup.2J.sub.P-C or .sup.3J.sub.P-C coupling constant of about 10.5 or 2.3 Hz. Another characteristic triplet signal at 209.5 ppm with a .sup.2J.sub.P-C coupling constant of about 12.0 Hz is assigned to the carbonyl carbon.

(47) Electrochemistry

(48) The redox behavior of 1,4-divinylphenylene-bridged diruthenium complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] was initially scrutinized by cyclic voltammetry (CV) and square-wave voltammetry (SWV) techniques to probe the electrochemical properties and the extend of the electronic interaction (coupling) between the two ruthenium vinyl moieties. The experiments were performed in CH.sub.2Cl.sub.2/n-NBu.sub.4.sup.+PF.sup. (0.1 M) as the supporting electrolyte. FIG. 3 shows the CV and SWV of the complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] in n-NBu.sub.4.sup.+PF.sup. recorded at a sweep rate of 0.1 V/s at r.t. versus the CP.sub.2Fe.sup.0/+ reference couple. Complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] undergoes two consecutive, chemically and electrochemically, well-behaved, reversible one-electron oxidations at well-accessible potentials. The half-wave redox splitting, E.sub.1/2=E.sub.1/2.sup.+/2+E.sub.1/2.sup.0/+, between their two individual redox one-electron E.sub.1/2=320 mV referring to strong electronic coupling communication between the two bis(ruthenium-alkenyl) moieties.

(49) IR Spectro-Electrochemistry

(50) IR spectroelectrochemistry (SEC) is a quantitative and an informative tool used in this study to get a crucial insight into the ruthenium-versus divinylphenylene bridge-based character of the individual redox processes. This can be fulfilled via investigating the changes in the energies and the band patterns for the degree of metal d/*(CO) backbonding upon accessible sequential oxidations, since those remarkable tokens are considered as an indicative measure of altering the electron density at the two rutheniumvinyl moieties. Complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] in its neutral state, shows classical intense vibrational bands at around 2900, 1880, 1550 cm.sup.1 assigned to the CH(aryl, alkyl), Ru(CO), and CC(vinyl, aryl) stretches, respectively. This low energy of the (CO) stretch band reflects, however, the high electron density at the two ruthenium-alkenyl moieties. First and second oxidations of complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] cleanly converted the neutral from to its corresponding mono- and di-cation in a stepwise fashion as indicated by distinct sets of isosbestic points. As a general scenario in stepwise fashion oxidation to the first radical cations of complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] led to replace the neutral Ru(CO) band at 1890 cm.sup.1 into a high a blue shift band at 1913 cm.sup.1 with a weak shoulder at 1927 cm.sup.1 as illustrated in FIGS. 4A and 4B. As the oxidation proceeded to the di-cation, the two CO bands of mixed-valent (MV) complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)]+ are again blued-shifted and merged into a single band at 1962 cm.sup.1. This typical observation pattern confirms a strongly coupled Class III system of Robin-Day classification of MV states.

(51) UV/Vis/NIR Spectroelectrochemistry

(52) Likewise all five-coordinated bis(ruthenium-alkenyl) complexes of the type {Ru}-arylene-{Ru} ({Ru}{Ru(CO)Cl(P.sup.iPr.sub.3).sub.2(CHCH)}), complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] as depicted in FIGS. 5A and 5B, features a main intense absorption UV-band at 350 nm which attributed to .fwdarw.* transitions within the extended metal-organic divinylarylene bridge chromophore and albeit prohibited, a typical weak characteristic Vis-band at 450 nm which assigned to an electronic transition within the d-manifold with the d-orbitals which gives the brilliant yellow color of this complex. Electrochemical oxidation was achieved by applying appropriate positive potentials to the complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] in NBu.sub.4.sup.+PF6.sup./CH.sub.2Cl.sub.2 in the UV/Vis/NIR regimes. Upon the first oxidation, the intensity of the UV-band of the neutral complex collapsed with the concomitant of growth of new intense band at the border of Vis/NIR region at 800 nm and strong NIR band between 1200 to 1600 nm. The NIR band is assigned to a .fwdarw.* transition within an open-shell, extended -system. As the oxidation proceeded to the di-cation [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)].sub.2.sup.+, both bands of [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)].sup.+ are disappeared and growth of new band is visible region. Thus complex [{Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2}.sub.2(-CHCHC.sub.6H.sub.4CHCH-1,4)] shows strong electrochromic behavior with at least three distinct states, as each individual oxidations are accompanied by the growth of intense absorption bands in the near infrared (NIR) and/or the visible (Vis) regime of electromagnetic radiation

(53) It is to be understood that the 1,4-divinylphenylene-bridged diruthenium complex bearing two Ru(CO)(8-mercaptoquinolato)(P.sup.iPr.sub.3).sub.2 moieties, compositions containing the same, and methods of using and producing the same are not limited to the specific embodiments described above, but encompasses any and all embodiments within the scope of the generic language of the following claims enabled by the embodiments described herein, or otherwise shown in the drawings or described above in terms sufficient to enable one of ordinary skill in the art to make and use the claimed subject matter.