US 6,515,084 B2Grant
High metathesis activity ruthenium and osmium metal carbene complexes
Issue Date:2003-02-04
•26 Claims
•2 Drawing Sheets
Abstract
Ruthenium and osmium carbene compounds that are stable in the presence of a variety of functional groups and can be used to catalyze olefin metathesis reactions on unstrained cyclic and acyclic olefins are disclosed. Also disclosed are methods of making the carbene compounds. The carbene compounds are of the formula
where M is Os or Ru; R1is hydrogen; R is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl; X and X1are independently selected from any anionic ligand; and L and L1are independently selected from any neutral electron donor. The ruthenium and osmium carbene compounds of the present invention may be synthesized using diazo compounds, by neutral electron donor ligand exchange, by cross metathesis, using acetylene, using cumulated olefins, and in a one-pot method using diazo compounds and neutral electron donors. The ruthenium and osmium carbene compounds of the present invention may be used to catalyze olefin metathesis reactions including, but not limited to, ROMP, RCM, depolymerization of unsaturated polymers, synthesis of telechelic polymers, and olefin synthesis.
Metadata
Assignee
- California Institute of Technology
Inventors
- Robert H. Grubbs
- Peter Schwab
- Sonbinh T. Nguyen
Application Information
Application Number:US 09/746,146
Filing Date:2000-12-21
Priority Date:1995-08-03
Art Unit:7
Classifications
IPC:
C08F 442C07F 902C07F 1500B01J 3100
Field of Search:
556 21556136556137502152502162526 90526 91526 92526 93526171526172526183526282526283
Patent Drawings (2 sheets)
Description
[0003] The present application is a divisional of U.S. application Ser. No. 09/399,963 filed Sep. 20, 1999, now U.S. Pat. No. 6,211,391, which is a divisional of issued U.S. application Ser. No. 09/007,498 filed Jan. 15, 1998, now U.S. Pat. No. 6,111,121, which is a divisional of issued U.S. application Ser. No. 08/693,789 filed Jul. 31, 1996, now U.S. Pat. No. 5,831,108, all of which are entitled HIGH METATHESIS ACTIVITY RUTHENIUM AND OSMIUM METAL CARBENE COMPLEXES by inventors Robert H. Grubbs, Peter Schwab, and Sonbinh T. Nguyen, the contents of each of which are herein incorporated by reference.
[0004] This application claims the benefit of U.S. Provisional application No. 60/001,862, filed Aug. 3, 1995, and U.S. Provisional application No. 60/003,973, filed Sep. 19, 1995, both of which are incorporated herein by reference.
BACKGROUND
[0006] This invention relates to highly active and stable ruthenium and osmium metal carbene complex compounds, their synthesis and use as catalysts for olefin metathesis reactions.
[0007] Transition-metal catalyzed C—C bond formation via olefin metathesis is of considerable interest and synthetic utility. Initial studies in this area were based on catalytically active mixtures consisting of transition-metal chlorides, oxides or oxychlorides, cocatalysts such as EtAlCl2or R4Sn, and promoters including O2, EtOH or PhOH. For example, WCl6/EtAlCl2/EtOH 1:4:1. These systems catalyze olefin metathesis reactions, however their catalytic centers are ill-defined and systematic control of their catalytic activity is not possible.
[0008] Recent efforts have been directed towards the development of well-defined metathesis active catalysts based on transition metal complexes. The results of research efforts during the past two decades have enabled an in-depth understanding of the olefin metathesis reaction as catalyzed by early transition metal complexes. In contrast, the nature of the intermediates and the reaction mechanism for Group VIII transition metal catalysts have remained elusive. In particular, the oxidation states and ligation of the ruthenium and osmium metathesis intermediates are not known.
[0009] Group VIII transition metal olefin metathesis catalysts, specifically ruthenium and osmium carbene complexes, have been described in U.S. Pat. Nos. 5,312,940 and 5,342,909 and U.S. patent application Ser. Nos. 08/282,826 and 08/282,827, all of which are incorporated herein by reference. The ruthenium and osmium carbene complexes disclosed in these patents and applications are of the general formula
[0010] where M is ruthenium or osmium, X and X1are anionic ligands, and L and L1are neutral electron donors. U.S. Pat. Nos. 5,312,940 and 5,342,909 disclose specific vinyl alkylidene ruthenium and osmium complexes and their use in catalyzing the ring opening metathesis polymerization (“ROMP”) of strained olefins. In all of the specific alkylidene complexes disclosed in these patents, R1is hydrogen and R is either a substituted or unsubstituted vinyl group. For example, a preferred vinyl alkylidene complex disclosed in these patents is
[0011] where Ph is phenyl.
[0012] U.S. patent application Ser. Nos. 08/282,826 and 08/282,827 disclose specific vinyl alkylidene ruthenium and osmium complexes and their use in catalyzing a variety of metathesis reactions. The catalysts disclosed in these applications have specific neutral electron donor ligands L and L1; namely, phosphines in which at least one substituent is a secondary-alkyl or cycloalkyl group. As in the above U.S. patents, in all of the specific alkylidene complexes disclosed in the patent applications, R1is hydrogen and R is either a substituted or unsubstituted vinyl group. For example, a preferred vinyl alkylidene complex disclosed in these patent applications is
[0013] where Cy is cyclohexyl.
[0014] Although the vinyl alkylidene complexes disclosed in the above patents and patent applications exhibit high metathesis activity and remarkable stability towards functional groups there are at least two drawbacks to these complexes as metathesis catalysts. First, the preparation of the vinyl alkylidene complexes requires a multi-step synthesis; and second, the vinyl alkylidene complexes have relatively low initiation rates. Both of these aspects of the vinyl alkylidene complexes are undesirable for their use as metathesis catalysts. The multi-step synthesis may be time consuming and expensive and may result in lower product yields. The low initiation rate may result in ROMP polymers with a broad molecular weight distribution and prolonged reaction times in ring closing metathesis (“RCM”) reactions.
[0015] For the reasons discussed above, there is a need for well-defined metathesis active catalysts that have the following characteristics: first, they are stable in the presence of a wide variety of functional groups; second, they can catalyze a variety of metathesis reactions including the metathesis of acyclic and unstrained cyclic olefins; third, they have a high initiation rate; and fourth, they are easily prepared. Furthermore, there is a need for olefin metathesis catalysts that can catalyze the ROMP of strained and unstrained cyclic olefins to yield polymers of very low polydispersity (i.e., PDI≈1.0) and that can catalyze the RCM of acyclic dienes with short reaction times.
SUMMARY
[0016] The present invention meets the above needs and provides well-defined ruthenium and osmium carbene compounds that are stable in the presence of a variety of functional groups and can be used to catalyze olefin metathesis reactions on unstrained cyclic and acyclic olefins. The compounds of the present invention are highly active in metathesis reactions and have high initiation rates.
[0017] In one embodiment of the present invention, the ruthenium and osmium carbene compounds have the formula
[0018] where M may be Os or Ru; R1is hydrogen; X and X1may be different or the same and are any anionic ligand; L and L1may be different or the same and are any neutral electron donor; and R may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl.
[0019] The ruthenium and osmium carbene complexes of the present invention are stable in the presence of a variety of functional groups. A consequence of this is that the alkyl and aryl R group may contain one or more functional groups including alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen groups.
[0020] R is preferably hydrogen, C1-20alkyl, or aryl. The C1-20alkyl may optionally be substituted with one or more aryl, halide, hydroxy, C1-20alkoxy, or C2-20alkoxycarbonyl groups. The aryl may optionally be substituted with one or more C1-20alkyl, aryl, hydroxyl, C1-5alkoxy, amino, nitro, or halide groups.
[0021] L and L1are preferably phosphines of the formula PR3R4R5, where R3is a secondary alkyl or cycloalkyl, and R4and R5are aryl, C1-10primary alkyl, secondary alkyl, or cycloalkyl. R4and R5may be the same or different.
[0022] L and L1are are most preferably the same and are —P(cyclohexyl)3, —P(cyclopentyl)3, or —P(isopropyl)3.
[0023] X and X1are most preferably the same and are chlorine.
[0024] In another embodiment of the present invention, the ruthenium and osmium carbene compounds have the formula
[0025] where M may be Os or Ru; X and X1may be different or the same and are any anionic ligand; L and L1may be different or the same and are any neutral electron donor; and R9and R10may be different or the same and may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl. The R9and R10groups may optionally include one or more of the following functional groups: alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen groups
[0026] The ruthenium and osmium carbene compounds of the present invention may be used to catalyze olefin metathesis reactions including, but not limited to, ROMP, RCM, depolymerization of unsaturated polymers, synthesis of telechelic polymers, and olefin synthesis.
[0027] In the ROMP reaction, a compound according to the present invention is contacted with a cyclic olefin to yield a ROMP polymer product. In the RCM reaction, a compound according to the present invention is contacted with a diene to yield a ring-closed product. In the depolymerization reaction, a compound according to the present invention is contacted with an unsaturated polymer in the presence of an acyclic olefin to yield a depolymerized product. In the synthesis of telechelic polymers, a compound according to the present invention is contacted with a cyclic olefin in the presence of an α,ω-difunctional olefin to yield a telechelic polymer. In the olefin synthesis reaction, a compound according to the present invention is contacted with one or two acyclic olefins to yield self-metathesis or cross-metathesis olefin products.
[0028] Since the ruthenium and osmium carbene compounds of the present invention are stable in the presence of a variety of functional groups, the olefins involved in the above reactions may optionally be substituted with one or more functional groups including alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen groups.
[0029] The above reactions may be carried out in aqueous, protic, or organic solvents or mixtures of such solvents. The reactions may also be carried out in the absence of a solvent. The reactants may be in the gas phase or liquid phase.
[0030] The ruthenium and osmium carbene compounds of the present invention may be synthesized using diazo compounds, by neutral electron donor ligand exchange, by cross metathesis, using acetylene, using cumulated olefins, and in a one-pot method using diazo compounds and neutral electron donors.
BRIEF DESCRIPTION OF DRAWINGS
[0031] The invention will be better understood by reference to the appended figures wherein:
[0032] FIGS. 1A and 1B are representative kinetic plots for acyclic metathesis of 1-hexene with RuCl2(═CHPh)(PCy3)2(complex 10) at 0° C.; and
[0033] FIG. 2 is an ORTEP plot of RuCl2(═CH-p-C6H4Cl)(PCy3)2(complex 15).
DETAILED DESCRIPTION
[0034] The abbreviations Me, Ph, iPr or i-Pr, Cy, Cp, n-Bu, and THF refer to methyl, phenyl, isopropyl, cyclohexyl, cyclopentyl, n-butyl, and tetrahydrofuran, respectively.
[0035] While previous investigations have explored the influence of the neutral electron donor and anionic ligands (i.e. L, L1, X, and X1) on the stability and utility of the ruthenium and osmium carbene complexes, the effect of variation of the alkylidene moieties (R and R1) had not been studied. By studying the effect of these substituents, it has been discovered that ruthenium and osmium complexes containing the specific alkylidene moieties of the present invention have unexpectedly high initiation rates compared to the vinyl alkylidene complexes previously described. Quantitative data is included below that demonstrates that the initiation rates of the complexes of the present invention are approximately a thousand times higher than the initiation rates of the corresponding vinyl alkylidene complexes. In addition to having unexpectedly high initiation rates, the complexes of the present invention are stable in the presence of a variety of functional groups and have high metathesis activity allowing them to catalyze a variety of metathesis reactions including metathesis reactions involving acyclic and unstrained cyclic olefins.
[0036] The compounds of the present invention are ruthenium and osmium alkylidene complexes of the general formula
[0037] where R1is hydrogen and R is selected from the specific group described below. Generally X and X1can be any anionic ligand and L and L1can be any neutral electron donor. Specific embodiments of X, X1, L, and L1are described in detail in U.S. Pat. Nos. 5,312,940 and 5,342,909 and U.S. patent application Ser. Nos. 08/282,826 and 08/282,827.
[0038] R may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl. The ruthenium and osmium carbene complexes of the present invention are stable in the presence of a variety of functional groups. A consequence of this is that the alkyl and aryl R groups may contain a variety of functional groups including alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen groups.
[0039] In a prefered embodiment R is hydrogen, C1-20alkyl, or aryl. The C1-20alkyl may optionally be substituted with one or more aryl, halide, hydroxy, C1-20alkoxy, or C2-20alkoxycarbonyl groups. The aryl may optionally be substituted with one or more C1-20alkyl, aryl, hydroxyl, C1-5alkoxy, amino, nitro, or halide groups. In a more prefered embodiment, R is hydrogen, C1-4alkyl, phenyl, C1-4alkyl substituted with one or more groups selected from the group consisting of halide, hydroxy, and C2-5alkoxycarbonyl, or phenyl substituted with one or more groups selected from the group consisting of C1-5alkyl, C1-5alkoxy, amino, nitro, and halide.
[0040] In a more preferred embodiment R may be hydrogen, methyl, ethyl, n-butyl, iso-propyl, —CH2Cl, —CH2CH2CH2OH, —CH2OAc, phenyl. The phenyl may optionally be substituted with a chloride, bromide, iodide, fluoride, —NO2, —NMe2, methoxy, or methyl group. In a more prefered embodiment, the phenyl is para-substituted.
[0041] In a most prefered embodiment R is phenyl.
[0042] Preferred complexes of the present invention include
[0043] where R is cyclohexyl, cyclopentyl, iso-propyl, or phenyl.
[0044] The most preferred complex of the present invention is
[0045] The ruthenium and osmium alkylidene complexes of the present invention may be synthesized by a variety of different methods including those taught in P. Schwab et al. Angew. Chem. Int. Ed. Engl. 34, 2039-2041 (1995), and P. Schwab et al. J. Am. Chem. Soc. 118, 100-110 (1996), both of which are incorporated herein by reference.
[0046] The ruthenium and osmium complexes of the present invention may be synthesized by alkylidene transfer from diazoalkanes. This synthetic method may generally be written as
[0047] where M, X, X1, L, L1, R and R1are as described above; m and n are independently 0-3 such that m+n=3; and p is a positive integer. In the diazo synthesis, a compound of the formula (XX1MLnL1m)pis contacted with a diazo compound of the formula RC(N2)R1to yield an alkylidene according to the present invention.
[0048] The ruthenium and osmium complexes of the present invention may also be synthesized by neutral electron donor ligand exchange as disclosed in U.S. Pat. Nos. 5,312,940 and 5,342,909 and U.S. patent Application Ser. Nos. 08/282,826 and 08/282,827.
[0049] The ruthenium and osmium complexes of the present invention may also be synthesized by cross metathesis. This method may generally be written as
[0050] where R11and R12may be the same or different and may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl.
[0051] The ruthenium and osmium complexes of the present invention may also be synthesized using acetylene reactants. This method may generally be written as
[0052] In the acetylene synthesis, a compound of the formula (XX1MLnL1m)pis reacted with an acetylene compound of the formula R9CCR10, to yield an alkylidene according to the present invention. R9and R10may be the same or different and may be hydrogen, substituted or unsubstituted alkyl, or substituted or unsubstituted aryl.
[0053] The ruthenium and osmium complexes of the present invention may also be synthesized using cumulated olefins. This method may generally be written as
[0054] The ruthenium and osmium complexes of the present invention may also be synthesized by a “one pot” method that can generally be written as
[0055] In this method, a compound of the formula (XX1MLnL1m)pis contacted with a diazo compound of the formula RC(N2)R1in the presence of a neutral electron donor L2to yield an alkylidene compound according to the present invention.
[0056] The catalysts of the present invention are highly active in metathesis reactions and may be used to catalyze a variety of metathesis reactions including, but not limited to, ROMP of strained and unstrained cyclic olefins, RCM of acyclic dienes, self- and cross-metathesis reactions involving at least one acyclic or unstrained cyclic olefin, depolymerization of olefinic polymers, acyclic diene metathesis polymerization (“ADMET”), alkyne polymerization, carbonyl olefination, and preparation of telechelic polymers.
[0057] ROMP, RCM, cross metathesis, depolymerization, and telechelic polymer reactions have been described in detail in U.S. patent application Ser. No. 08/282,827. Those skilled in the art can readily identify the appropriate conditions for carrying out these reactions using the complexes of the present invention. Any specific differences between the reactions disclosed in patent application No. 08/282,827 and those of the present invention are noted in the detailed descriptions given below.
[0058] Alkyne polymerization is described by R. Schlund et al. in J. Am. Chem. Soc.1989, 111, 8004-8006, and by L. Y. Park et al. in Macromolecules1991, 24 3489-3495, both of which are incorporated herein by reference. Carbonyl olefination is described by K. A. Brown-Wensley et al. in Pure Appl. Chem.1983, 55, 1733-1744, by A. Aguero et al. in J. Chem. Soc., Chem. Commun.1986, 531-533, and by G. C. Bazan et al. in Organometallics1991, 10, 1062-1067, all of which are incorporated herein by reference. ADMET is described by K. B. Wagener et al. in Macromolecules1991, 24, 2649-2657, which is incorporated herein by reference. Those skilled in the art can readily identify the appropriate conditions for carrying out these reactions using the complexes of the present invention.
[0059] We now describe specific examples of the synthesis and olefin metathesis reactions described above. For clarity, detailed reaction conditions and procedures are described in the final, “Experimental Procedures” section.
SYNTHESIS OF ALKYLIDENE COMPLEXES
[0060] Synthesis of RuCl2(═CHR)(PPh3)2via Alkylidene Transfer from Diazoalkanes (Complexes 1-9)
[0061] The alkylidene complexes of the present invention may be synthesized by the reaction of RuCl2(PPh3)3with alkyl, aryl, and diaryidiazoalkanes. Generally, the synthesis reactions involve a spontaneous N2evolution at −78° C., indicating rapid reaction of RuCl2(PPh3)3with diazoethane, diazopropane or a para-substituted aryldiazoalkane of the formula p-C6H4XCHN2to give RuCl2(═CHR)(PPh3)2(R═Me [complex 1], Et [complex 2]) and RuCl2(═CH-p-C6H4X)(PPh3)2(X═H [complex 3], NMe2[complex 4], OMe [complex 5], Me [complex 6], F [complex 7], Cl [complex 8], NO2[complex 9 ]), respectively (eq. 1). However, no reaction was observed with diphenyldiazomethane or 9-diazofluorene at RT, and reaction with diazomethane led to a complex mixture of unidentified products.
[0062] Complexes 1-9 were isolated in 80-90% yield as green air-stable solids. In all of these reactions, transfer of the alkylidene moiety from the diazo compound to ruthenium was clearly indicated by the characteristic downfield-resonances of Hαand Cαof the alkylidene moiety. Table I below lists selected NMR data for complexes 3-9.
| TABLE I | |||||
|---|---|---|---|---|---|
| Complex | X | H | J | C | J |
[0063] In analogy to the structurally characterized vinyl alkylidene RuCl2(═CH—CH═CPh2) (PPh3)2(Complex A), these resonances appear as triplets due to 31P coupling. These spectroscopic data suggest that the phosphines are mutually trans and that the alkylidene unit lies in the P-Ru-P-plane. Additionally, the chemical shifts of Hαand Cαin complexes 3-9 are downfield compared to RuCl2(═CH—CH═CPh2)(PPh3)2(Complex A) (δHα=17.94, Cα=288.9 ppm), possibly attributed to the relatively reduced conjugation of the alkylidene unit of complexes 3-9. This phenomenon might also be responsible for the relative instability of complexes 1-9 in solution. These complexes decompose within several hours via bimolecular pathways as evidenced by the formation of the corresponding disubstituted olefins RCH═CHR (R═Me, Et, p-C6H4X).
Synthesis of RuCl
[0064] To broaden the synthetic utility of the triphenylphosphine catalysts, analogous trialkylphosphine derivatives of complexes 3-9 were prepared by phosphine exchange. Treatment of complexes 3-9 with 2.2 equiv. tricyclohexylphosphine at RT afforded, after work-up, RuCl2(═CH-p-C6H4X)(PCy3)2(X ═H [complex 10], NMe2[complex 11], OMe [complex 12], Me [complex 13], F [complex 14], Cl [complex 15], NO2[complex 16]), as purple (complex 11 is green) microcrystalline solids in high yields according to the following reaction:
[0065] The fully-characterized compounds were air-stable in the solid state and did not show any signs of decomposition in solution (CH2Cl2or C6H6), even when heated to 60° C. or in presence of alcohols, amines or water. Selected solution NMR data for complexes 10-16 are listed in Table II. As can be seen from this data, in contrast to the PPh3complexes 3-9, no 31P coupling was observed for the Hαresonances of complexes 10-16 in the 1H NMR. The chemical shifts of these resonances are dependent on the electronic nature of the X substituent.
| TABLE II | ||||
|---|---|---|---|---|
| Complex | X | H | C | J |
| 10 | H | 20.02 | 294.72 | 7.6 |
| 11 | NMe | 18.77 | 286.13 | a |
| 12 | OMe | 19.48 | 290.90 | a |
| 13 | Me | 19.80 | 293.86 | 8.3 |
| 14 | F | 19.86 | 291.52 | 8.6 |
| 15 | Cl | 19.98 | 291.46 | 8.0 |
| 16 | NO | 20.71 | 289.07 | 7.6 |
[0066] The lack of 31p coupling suggests that the alkylidene moiety is perpendicular to the P-Ru-P-plane as in RuCl2(═CH—CH═CPh2)(PCy3)2(Complex B). Also, the resonance shifts' dependency on the electronic nature of the X substituent suggests a high degree of conjugation between the carbene carbon and the aromatic ring of the benzylidene moiety.
One-pot Synthesis of RuCl
[0067] Due to the relative instability of the intermediate RuCl2(═CHPh)(PPh3)2(complex 3) in solution, RuCl2(═CHPh)(PCy3)2(complex 10) can be synthesized in 75-80% yield from RuCl2(PPh3)3. However, avoiding isolation of complex 3 and adding tricyclohexylphosphine at ≈−50° C. shortly after RuCl2(PPh3)3was treated with phenyidiazomethane, complex 10 can be obtained in nearly quantitative yield in less than 1 hour in a so-called “one pot synthesis”. The same procedure can also be applied to the synthesis of more soluble derivatives including RuCl2(═CHPh)(PR3)2where R is Cp (complex 17) or R is iPr (complex 18) that exhibit comparable metathesis activity, according to the following reaction:
[0068] Synthesis of Methylidene Complex RuCl2(═CH2)(PCy3)2(Complex 19)
[0069] Whereas RuCl2(═CH—CH═CPh2)(PCy3)2(Complex B) reacts with ethylene under 100 psi pressure at 50° C. in CD2Cl2within several hours to reach an equilibrium of RuCl2(═CH—CH═CPh2)(PCy3)2(Complex B) and RuCl2(═CH2)(PCy3)2(complex 19) in a ratio of 80:20, benzylidene RuCl2(═CHPh)PCy3)2(complex 10) is quantitatively converted to the methylidene complex 19 within a few minutes at RT under 14 psi of ethylene (eq. 7).
[0070] Complex 19 is isolated as a red-purple, air-stable solid. A pentacoordinate ruthenium center may be inferred from the analytic and spectroscopic data. Methylidene complex 19 is less stable in solution than benzylidene complex 10; decomposition is observed after 12 hours in solution (CH2Cl2, C6H6). The decomposition rate increases as catalyst solutions are heated. Among all isolated methylidene complexes including RuCl(NO)(CH2)(PPh3)2and lr═CH2(N(SiMe2—CH2PPh2(2), complex 19 is the first isolable metathesis-active methylidene complex. Complex 19 has a high activity and exhibits a similar stability towards functional groups as benzylidene complex 10, as shown in the ROMP of cyclooctene and 1,5-cyclooctadiene and in ring-closing metathesis of diethyidiallyl malonate.
[0071] Synthesis of substituted alkylidene complexes via cross metathesis
[0072] The rapid reaction of RuCl2(═CHPh)(PCy3)2(complex 10) with ethylene to give RuCl2(═CHPh)(PCy3)2(complex 19) has prompted extension by the inventors of these metathesis studies to terminal and disubstituted olefins. Although olefin metathesis is an equilibrium process, the kinetic products may be isolated under certain conditions. Indeed, complex 10 is quantitatively converted to the alkylidenes according to the formula RuCl2(═CHR)(PCy3)2[R═Me (complex 20), R═Et (complex 21), R═n-Bu (complex 22)] when reacted with a tenfold excess of propene, 1-butene or 1-hexene, respectively. In each case, an equimolar amount of styrene was formed and spectroscopically identified (eq. 4).
[0073] The isolated compounds 20-22 are comparable to precursor complex 10 in stability and solubility and reconvert to precursor complex 10 in the presence of a large excess (30-50 equiv.) of styrene. Metathesis of disubstituted olefins cis-2-butene and cis-3-hexene leads to the formation of RuCl2(═CHR)(PCy3)2from benzylidene complex 10. However, due to the steric bulk of these olefins, the reactions proceed considerably slower than with the corresponding terminal olefins. No reaction occurred between precursor complex 10 and 3,3-dimethyl-1-butene, and stearic interaction between the metal fragment and the incoming olefin is also presumed to be responsible for the slow reaction with 20 equiv. 3-methyl-1-butene. The expected alkylidene RuCl2(═CHR)(PCy3)2was identified by NMR, but its concentration remained small and constant throughout the reaction. After 6 hours, initiation was complete and methylidene complex 19 was isolated as the sole reaction product. If alkylidene forms of RuCl2(═CHR)(PCy3)2of complexes 20-22 are not isolated immediately after formation, slow reaction with excess olefin results in the formation of RuCl2(═CH2)(PCy3)2(complex 19) within 10-15 hours (eq. 8).
[0074] As proposed in the reaction scheme l below, complex 10 is likely to react with a terminal olefin to rapidly form a metallocyclobutane intermediate l, in that the two substituents (Ph and R) are in 1,3-position for stearic reasons. Productive cleavage of the intermediate metallacycle leads to the formation of alkylidene complexes 20-22 as kinetic products.
[0075] On extended reaction times, alkylidene complexes RuCl2(═CHR)(PCy3)2(complexes 20-22) undergo a slow reaction with excess olefin to form methylidene complex 19 presumably through intermediate metallocyclobutane II. RuCl2(═CH2)(PCy3)2(complex 19) appears to be the thermodynamic product as it will not metathesize α-olefins in dilute conditions.
[0076] Metathesis of conjugated and cumulated olefins
[0077] Treatment of RuCl2(═CHPh)(PCy3)2(complex 10) with a tenfold excess of 1,3-butadiene and 1,2-propadiene resulted in the high-yield formation of vinylalkylidene RuCl2(═CH—CH═CH2)(PCy3)2(complex 23) and vinylidene RuCl2(═C═CH2)(PCy3)2(complex 24), respectively (eq. 5). The former complex cannot be synthesized via ring-opening of cyclopropene.
[0078] The spectroscopic data for these complexes is similar to those of related compounds RuCl2(═CH—CH═CPh2)(PCy3)2(complex B) and RuCl2(═C═CH-t-Bu)(PPh3)2. In contrast to observations made in the synthesis of RuCl2(═CHR)(PCy3)2[R═Me (complex 20), Et (complex 21), n-Bu (complex 22)], that no methylidene RuCl2(═CH2)(PCy3)2(complex 19) was formed at extended reaction times can be explained by the low activity of complexes 23 and 24 towards their olefinic precursors. However, both complexes 23 and 24 exhibit ROMP-activity that, in the case of the former, was evidenced by comparatively slow polymerization of cyclooctene (PDI=2.0). Vinylidene complex 24 rapidly polymerized norbornene, although relatively slow initiation can be inferred by the lack of the characteristic color change, and both compounds are inactive for metathesis of acyclic olefins.
[0079] Introduction of functional groups via metathesis
[0080] Although less active than their early transition metal counterparts, ruthenium alkylidenes have broader synthetic utility due to their tolerance of functional groups and protic media. The inventors have shown that vinylalkylidenes RuCl2(═CH—CH═CPh2)(PR3)2(R═Ph, complex A; or R═Cy, complex B) react readily with electron-rich olefins, such as vinyl ethers H2C ═CH—OR′, to yield metathesis-inactive RuCl2(═CH—OR′)(PR3)2. This irreversible reaction has been extensively utilized by the inventors for the endcapping of growing polymer chains. Electron-deficient olefins are not metathesized by the triphenylphosphine catalyst RuCl2(═CH—CH═CPh2)(PPh3)2(complex A), and the tricyclohexylphosphine catalyst RuCl2(═CH—CH═CPh2)(PCy3)2(complex B) displays only limited activity towards these substrates. However, the enhanced activity of the benzylidene catalyst complex 10 prompted further exploration of this reaction. As shown in eq. 6, metathesis of functionalized olefins catalyzed by benzylidene complex 10 is not limited to electron-rich olefins, such as allyl acetate, but also includes electron-deficient alkenes, such as allyl chloride. Benzylidene complex 10 will also undergo efficient metathesis of unprotected en-ols, as shown with 4-pentene-1-ol, to generate the corresponding hydroxy alkylidene RuCl2(═CH(CH2)3OH)(PCy3)2(complex 27) (eq. 6).
[0081] Compounds 25-27 were readily isolated and fully characterized. In all cases the alkylidene Hαresonances appeared as triplets due to coupling with the vicinal CH2groups. Alkylidenes 25-27 are active in ROMP of low strained olefins, which makes them attractive catalysts for the synthesis of telechelic and other functionalized polymers.
[0082] USE OF ALKYLIDENE COMPLEXES AS METATHESIS CATALYSTS
[0083] Kinetic studies of the polymerization of norborene catalyzed by RuCl2(═CH-p-C6H4X)(PPh3)2(Complexes 3-9)
[0084] Complexes 3-9 polymerize norbornene at a rate of ≈150 equiv./hour in CH2Cl2at RT to give polynorbornene in quantitative yields. All reactions were accompanied by a characteristic color change from green-brown to orange that indicates complete initiation. The resulting polymers are approximately 90% trans as determined by 1H NMR. However, the present catalysts produce nearly monodispersed polymers (PDls =1.04-1.10, compared to 1.25 for RuCl2(═CH—CH═CPh2)(PPh3)2) (complex A), consistent with measured initiation rates. As observed for RuCl2(═CH—CH═CPh2)(PPh3)2(complex A), complexes 3-9 fulfill the general criteria for living systems since the propagating alkylidene (1H NMR: δ17.79 ppm (dt)) is stable throughout the reaction, and the molecular weights of the polymers display a linear dependence on the [catalyst]/[monomer] ratio.
[0085] The influence of the para-substituents in the alkylidene moiety on the metathesis activity was qualitatively assessed. Catalysts based on complexes 3-9 (RuCl2(═CH-p═C6H4X)(PPh3)2, [Ru] =0.022 M) were treated with norbornene ([monomer] =0.435 M) in CH2Cl2solution. The pseudo first-order rate constants for initiation and propagation were obtained by integrating the Hαresonances of complexes 3-9 against the corresponding resonance of the propagating alkylidene species, and monitoring the decreasing monomer concentration against an internal ferrocene standard, respectively. The derived values of kiand kpare listed in Table III.
| TABLE III | ||||
|---|---|---|---|---|
| Initiation Rate | Propagation Rate | |||
| Constant, k | Constant, k | |||
| Complex | X | (×10 | (×10 | k |
[0086] As can be seen in Table III, the electronic effect of X in RuCl2(═CH-p-C6H4X)(PPh3)2on initiation rate seems to be relatively small: the rate in the fastest case (X=H [complex 3]) was approximately 10 times higher than in the slowest (X=Cl [complex 8]). A general trend concerning the electronic influence of the substituents X was not observed. Under similar reaction conditions with RuCl2(═CH—CH═CPh2)(PPh3)2(complex A) as catalyst, observed initiation was <50%. When norbornene consumption was complete, uninitiated carbene was spectroscopically identified. The extrapolated ratio of kj/kp=6×10−3is approximately 1000 times smaller than that observed for complexes 3-9. These results suggest that conjugation seems to decrease ki, presumably by lowering the ground state energy of the starting arylidenes for complexes 3-9 relative to the likely metallocyclobutane intermediate. Although benzylidene forms of complexes 3-9 are better initiators than RuCl2(═CH—CH═CPh2)(PPh3)2(Complex A), application of the former as metathesis catalysts is similarly limited to ROMP of relatively high-strained cyclic olefins, such as norbornene and cyclobutene derivatives, whose calculated strain energies exceed 10-15 kcal/mol.
[0087] ROMP activity of RuCl2(═CH-p-C6H4X)(PCy3)2(complexes 10-16)
[0088] Benzylidenes RuCl2(═CH-p-C6H4X)(PCy3)2(complexes 10-16) are extremely active ROMP-catalysts compared to their PPh3analogs complexes 3-9. Except for norbornene, ROMP of highly strained monomers including functionalized norbornenes, 7-oxanorbornenes, and variously substituted cyclobutenes was proved to be living and lead to polymers with exceptionally narrow molecular weight distributions (PDIs<1.1). In analogy to RuCl2(═CH—CH═CPh2)(PCy3)2(complex B), complexes 10-16 can also polymerize low-strain cycloolefins, such as cyclooctene and 1,5-cyclooctadiene. Although the corresponding polymers are not monodispersed (PDI≈1.50-1.60), these polymerizations proceed more rapidly and with significantly lower polydispersities than with RuCl2(═CH—CH═CPh2)(PCy3)2(complex B) as catalyst (PDI≈2.50). However, the occurrence of “back-biting” in these reactions causes broader PDIs. Therefore, these polymerizations cannot be considered living, even though a propagating alkylidene was observed for ROMP of cyclooctadiene by 1H NMR (δ18.88 (t)) with complex 10.
[0089] Complex 10 also reacts with cyclooctatetraene in CD2Cl2with complete initiation, but propagation does not occur, and facile back-biting leads to the formation of benzene. The increased activity of complexes 10-16 compared to RuCl2(═CH—CH═CPh2)(PCy3)2(Complex B) is attributed to a faster initiation rate. Recently developed catalyst mixtures containing [(cymene)RuCl2]2, a bulky tertiary phosphine and trimethylsilyidiazomethane were found to catalyze ROMP of cyclooctenes.
[0090] Metathesis of Acyclic Olefins
[0091] The inventors recently showed that vinylalkylidene RuCl2(═CH—CH═CPh2)(PCy3)2(Complex B) exhibits metathesis activity towards acyclic olefins, e.g., cis-2-pentene. Although the turnover-numbers were modest compared to the best of the tungsten and molybdenum-based catalysts, vinylalkylidene RuCl2(═CH—CH═CPh2)(PCy3)2(complex B) was the first example of acyclic metathesis induced by a ruthenium carbene complex. However, slow initiation was a present limitation for its general use as a catalyst. Due to their exceptionally high activity in ROMP, complexes 10-16 were found to be efficient acyclic metathesis catalysts, as representatively shown with benzylidene RuCl2(═CHPh)(PCy3)2(complex 10), discussed below.
[0092] Kinetic studies with RuCl2(═CH-p-C6H4X)(PCy3)2(Complexes 10-16)
[0093] The electronic influence of X on the initiation rates of RuCl2(═CH-p-C6H4X)(PCy3)2(complexes 10-16) was probed by examining their reactions with 1-hexene. Clean and quantitative conversion to the pentylidene RuCl2(═CH—n—Bu)(PCy3)2complex 22 was observed in all cases. Pseudo first-order rate constants were measured by integration of the Hα resonances of benzylidene complexes 10-16 versus pentylidene complex 22. Representative plots are shown in FIGS. 1A and 1B, and initiation rate constants (ki) are listed in Table IV.
| TABLE IV | ||
|---|---|---|
| Initiation Rate Constant | ||
| Complex | X | k |
| 10 | H | 2.87 |
| 11 | NMe | 0.31 |
| 12 | OMe | 1.01 |
| 3 | Me | 2.15 |
| 14 | F | 1.21 |
| 15 | Cl | 1.37 |
| 16 | NO | 1.77 |
[0094] As observed for living-ROMP of norbornene with catalysts RuCl2(═CH-p-C6H4X)(PPh3)2(complexes 3-9), the range of kis among the substituted benzylidenes is approximately an order of magnitude. Although no general trend can be discerned, any perturbation to the aromatic π-system (i.e., X ≠H) decreases the initiation rate. RuCl2(═CHPh)(PCy3)2(complex 10) initiated approximately 1000 times faster than vinylidene RuCl2(═CH—CH═CPh2)(PCy3)2(Complex B) which did not completely react to give pentylidene complex 22 under the above-mentioned conditions.
STRUCTURE OF EXEMPLARY COMPLEX
[0095] X-ray diffraction study of RuCl2(═CH-p-C6H4Cl)(PCy3)2(Complex 15)
[0096] Representative of complexes 10-16, the structure of the Cl-substituted benzylidene RuCl2(═CH-p-C6H4Cl)(PCy3)2was further confirmed by a single crystal X-ray diffraction-study. An ORTEP drawing of this complex is shown in FIG. 2, and selected bond lengths and angles are given in Table V below. The analysis reveals distorted square-pyramidal coordination with a nearly linear Cl(1)—Ru—Cl(2) angle (167.61°). The carbene unit is perpendicular to the P1—Ru—P2 plane, and the aryl ligand is only slightly twisted out of the Cl1—Ru—Cl2 plane. The Ru—C1 bond distance is shorter (1.838(3) Å) than in related compounds RuCl2(═CH—CH═CPh2)(PCy3)2[d(Ru—C) =1.851(21)] or RuCl(═C(OMe)—CH ═CPh2)(CO)(Pi—Pr3)2[RuCl2(═CH—CH═CPh2)(PCy3)2F4] [d—(Ru—C)=1.874(3), respectively.
| TABLE V |
|---|
| Bond Lengths [Å] |
EXPERIMENTAL SECTION
[0097] General Experimental Procedures
[0098] All manipulations were performed using standard Schlenk techniques under an atmosphere of argon. Argon was purified by passage through columns of BASF R3-11 catalyst (Chemalog) and 4Å molecular sieves (Linde). Solid organometallic compounds were transferred and stored in a nitrogen-filled Vacuum Atmospheres drybox or under an atmosphere of argon. NMR spectra were recorded with either a QE-300 Plus (300.1 MHz 1H; 75.5 MHz 13C), a JEOL GX-400 (399.7 MHz 1H; 161.9 MHz 31p) or a Bruker AM 500 (500.1 MHz 1H; 125.8 MHz 13C; 202.5 MHz 31p; 470.5 MHz 19F) spectrometer.
[0099] Methylene chloride and benzene were passed through columns of activated alumina and stored under argon. Benzene-d6and methylene chloride-d2were degassed by three continuous freeze-pump-thaw cycles. RuCl2(PPh3)3, tricyclohexylphosphine, and the diazoalkanes H2CN2, MeCHN2, EtCHN2, PhCHN2, p-C6H4NMe2CHN2, p-C6H4OMeCHN2, p-C6H4MeCHN2, p-C6H4FCHN2, p-C6H4ClCHN2and p-C6H4NO2CHN2were prepared according to literature procedures. Norbornene was dried over sodium, vacuum transferred and stored under argon. Cyclooctene, 1,5-cyclooctadiene, and 1,3,5,7-cyclooctatetraene were dried over CaH2, distilled and stored under argon. The following chemicals were obtained from commercial sources and used as received: ethylene, propylene, 1-butene, cis-2-butene, 1-hexene, cis-3-hexene, 3-methyl-1-butene, 3,3-dimethyl-1-butene, 1,3-butadiene, 1,2-propadiene, allyl acetate, allyl chloride, 4-pentene-2-ol, diethyl diallyl malonate, triisopropylphosphine, tricyclo-pentylphosphine, pentane, ether, acetone, and methanol.
[0100] Synthesis of RuCl2(═CHMe)(PPh3)2and RuCl2(═CHEt)(PPh3)2(Complexes 1 and 2)
[0101] A solution of RuCl2(PPh3)3(417 mg, 0.43 mmol) in CH2Cl2(10 mL) was treated at −78° C. with a −50° C. 0.50 M solution of diazoethane (1.90 mL, 0.93 mmol, 2.2 eq.) in ether. Upon addition of diazoethane, a color change from orange-brown to green-brown and slight bubbling were observed. After the cooling bath was removed, the solution was stirred for 3 min and then evaporated to dryness. The oily residue was washed several times with small quantities of ice-cold ether (3 mL portions) and the remaining olive-green solid RuCl2(═CHMe)(PPh3)2was dried under vacuum for several hours. Yield ═246 mg (78%). 1H NMR (CD2Cl2): δ18.47 (tq, JPH=10.2 Hz, 3JHH=5.1 Hz, Ru═CH), 7.68-7.56 and 7.49-7.36 (both m, P(C6H5)3), 2.59 (d, 3JHH5.1 Hz, CH3). 13C NMR (CD2Cl2): δ320.65 (t, JPC=9.9 Hz, Ru ═CH), 134.76 (m, o-C of P(C6H5)3), 132.06 (m, ipso-C of P(C6H5)3), 130.38 (s, p-C of P(C6H5)3), 128.44 (m, m-C of P(C6H5)3). 31P NMR (CD2Cl2): δ6 29.99 (s, PPh3). Anal. Calcd. for C38H34Cl2P2Ru: C, 62.99; H, 4.73. Found: C, 63.12; H, 4.61.
[0102] In an analogous procedure, RuCl2(═CHEt)(PPh3)2was prepared, starting with RuCl2(PPh3)3(502 mg, 0.52 mmol) and a 0.45 M solution of diazopropane (2.56 mL, 1.15 mmol, 2.2 eq.) in ether. An orange-brown microcrystalline solid was obtained. Yield =311 mg (81%). 1H NMR (C6D8): δ18.21 (tt, JPH=10.8, 3JHH6.6 Hz, Ru═CH), 7.91-7.86 and 6.97-6.80 (both m, P(C6H5)3), 3.11 (dq, 3JHH=3JHH′=6.6 Hz, CH2CH3), 0.79 (t, 3JHH=6.6 Hz, CH2CH3). 13C NMR (CD2Cl2): δ320.88 (t, JPC=10.0 Hz, Ru═CH), 134.36 (m, o-C of P(C6H5)3, 132.27 (m. ipso-C of P(C6H5)3), 129.89 (s, p-C of P(C6H5)3), 128.14 (m, m—C of P(C6H5)3), 53.20 (s, CH2CH3), 29.74 (s, CH2CH3). 31P NMR (CD2Cl2): δ30.02 (s, PPh3). Anal. Calcd. for C39H36Cl2P2Ru: C, 63.42; H, 4.91. Found: C, 62.85; H, 4.81.
[0103] Synthesis of RuCl2(═CHPh)(PPh3)2(Complex 3)
[0104] A solution of RuCl2(PPh3)3(2.37 g, 2.47 mmol) in CH2Cl2(20 mL) was treated at −78° C. with a −50° C. solution of phenyldiazomethane (584 mg, 4.94 mmol, 2.0 eq.) in CH2Cl2or pentane (3 mL). A spontaneous color change from orange-brown to brown-green and vigorous bubbling were observed. After the cooling bath was removed, the solution was stirred for 5 min and the solution was then concentrated to ˜3 mL. Upon addition of pentane (20 mL), a green solid was precipitated, separated from the brown mother-liquid via cannula filtration, dissolved in CH2Cl2(3 mL) and reprecipitated with pentane. This procedure was repeated until the mother-liquid was nearly colorless. The remaining grey-green microcrystalline solid was dried under vacuum for several hours. Yield =1.67 g (89%). 1H NMR (C6D6): δ19.56 (t, JPH=10.2 Hz, Ru═CH), 7.80-7.64 and 6.99-6.66 (both m, C6H5and P(C6H5)3). 13C NMR (CD2Cl2): δ310.12 (t, JPC=11.4 Hz, Ru═CH), 155.36 (s, ipso-C of C6H5), 134.91 (m, m-C or o-C of P(C6H5)3), 133.97 (d, JPC19.6 Hz, ipso-C of P(C6H5)3), 130.44 (s, p-C of P(C6H5)3), 130.03, 128.71 and 127.09 (all s, C6H5), 128.37 (s(br.), m-C or o-C of P(C6H5)3). 31p NMR (CD2Cl2): δ30.63 (s, PPh3). Anal. Calcd. for C43H36Cl2P2Ru: C, 65.65; H, 4.61; P. 7.87. Found: C, 65.83; H, 4.59; P, 7.93.
[0105] Synthesis of RuCl2(═CH-p-CeH4NMe2)(PPh3)2(Complex 4)
[0106] A solution of RuCl2(PPh3)3(466 mg, 0.49 mmol) in CH2Cl2(10 mL) was treated at −78° C. with a −50° C. solution of p-C6H4NMe2CHN2(160 mg, 0.98 mmol, 2.0 eq.) in CH2Cl2(3 mL). A spontaneous color change from orange-brown to brown-green and vigorous bubbling was observed. After the cooling bath was removed, the solution was stirred for 10 min and then the solvent was removed under vacuum. The brown residue was dissolved in minimal amounts of CH2Cl2(3 mL), and pentane (20 mL) was added to precipitate a green solid. After cannula filtration, this procedure was repeated until the filtrate was colorless. The remaining olive-green microcrystalline solid was dried under vacuum for several hours. Yield=317 mg (78%). 1H NMR (CD2Cl2): δ18.30 (t, JPH=6.1 Hz, Ru═CH), 7.64 (d, 3JHH=8.7 Hz, o—H of C6H4NMe2), 7.52-7.49 (m, o—H of P(C6H5)3), 7.42 (t, 3JHH=7.5 Hz, p—H of P(C6H5)3=7.33 (t, 3JHH=7.5 Hz, m—H of P(C6H5)3), 6.32 (d, 3JHH=8.7 Hz, m—H of C6H4NMe2), 2.96 (s, N(CH3)2). 13C NMR (CD2Cl2): δ309.68 (t, JPC11.4 Hz, Ru═CH), 152.72 (s, ipso-C of C6H4NMe2), 135.01 (m, m-C or o-C of P(C6H5)3), 133.57 (s, o-C or m-C of C6H4NMe2), 131.86 (s, C of P(C6H5)3), 130.20 (s, o-C or m-C of C6H4NMe2), 128.27 (m, m-C or o-C of P(C6H5)3), 127.54 (s(br.), p-C of C6H4NMe2), 110.61 (d, JPC=21.5 Hz, ipso-C of P(C6H5)3, 40.30 (s, N(CH3)2. 31P NMR (CD2Cl2): δ34.84 (s, PPh3). Anal. Calcd. for C45H41Cl2NP2Ru: C, 65.14; H, 4.98; N, 1.69. Found: C, 65.28; H, 4.97; N 1.80.
[0107] Synthesis of RuCl2(═CH-p-C6H4OMe)(PPh3)2(Complex 5)
[0108] A solution of RuCl2(PPh3)3(561 mg, 0.59 mmol) in CH2Cl2(12 mL) was treated at −78° C. with a −40° C. solution of p-C6H4OMeCHN2(87 mg, 0.59 mmol, 1.0 eq.) in CH2Cl2(3 mL). A spontaneous color change from orange-brown to brown-green and vigorous bubbling was observed. After the cooling bath was removed, the solution was stirred for 5 min and then the solvent was removed under vacuum. The brown-green residue was dissolved in minimal amounts of CH2Cl2(2 mL), and pentane (20 mL) was added to precipitate a brown solid. The brown-green solution was separated via cannula filtration and dried under vacuum. The remaining olive-green solid, complex 5, was repeatedly washed with ether (10 mL portions) and dried under vacuum for several hours. Yield w. 400 mg (83%). 1H NMR (C6D6): δ19.39 (t, JPH=8.7 Hz, Ru═CH), 7.85-7.72 and 7.03-6.80 (both m, C6H4OMe and P(C6H5)3, 6.41 (d, 3JHH=8.7 Hz, m—H of C6H4OMe), 3.22 (s, OCH3). 13C NMR (CD2Cl2); δ309.20 (t, JPC=10.7 Hz, Ru═CH), 147.42 (s, ipso-C of C6H4OMe), 135.56 (pseudo—t, m-C or o-C of P(C6H5)3, 133.98 (s, o-C or m-C of C6H4OMe), 131.46 (s, p-C of P(C6H5)3), 130.43 (s, o-C or m-C of C6H4OMe), 128.40 (pseudo-t, m-C or o-C of P(C6H5)3, 126.82 (s, p-C of C6H4OMe), 113.95 (d, JPC=21.4 Hz, ipso-C of P(C6H5)3, 55.77 (s, OCH3). 31p NMR (CD2Cl2): δ32.50 (s, PPh3). Anal. Calcd. for C44H38Cl2OP2Ru: C, 64.71; H, 4.69. Found: C, 65.23; H, 4.78.
[0109] Synthesis of RuCl2(═CH-p-C6H4Me)(PPh3)2(Complex 6)
[0110] In a technique analogous to that used in synthesizing complex 5, RuCl2(═CH-p-C6H4Me)(PPh3)2was prepared from RuCl2(PPh3)3(350 mg, 0.37 mmol) and p-CeH4MeCHN2(48 mg, 0.37 mmol, 1.0 eq.) A brown microcrystalline solid was obtained. Yield =258 mg (87%). 1H NMR (C6D6): δ19.55 (t, JPH=9.6 Hz, Ru═CH), 7.84-7.63 and 7.02-6.80 (both m, C6H4Me and P(C6H5)3), 6.53 (d, 3JHH=7.8 Hz, m-H of C6H4Me), 1.68 (s, CH3). 13C NMR (CD2Cl2): δ309.17 (t, JPC=10.9 Hz, Ru═CH), 153.34 (s, ipso-C of C6H4Me), 135.50 (s, o-C or m-C of C6H4OMe), 134.96 (m, m-C or o-C of P(C6H5)3, 132.13 (s, p-C of P(C6H5)3), 130.39 (s, o-C or m-C of C6H4Me), 128.34 (m, m-C or o-C of P(C6H5)3), 126.76 (s, p-C of C6H4Me), 115.23 (d, JPC=21.4 Hz, ipso-C of P(C6H5)3), 40.92 (s, CH3). 31P NMR (CD2Cl2): δ31.29 (s, PPh3). Anal. Calcd. for C44H38Cl2P2Ru: C, 66.00; H, 4,78. Found: C, 65.90; H, 4.75.
[0111] Synthesis of RuCl2(═CH-p-C6H4F)(PPh3)2(Complex 7)
[0112] In a technique analogous to that used in synthesizing complex 3, RuCl2(═CH-p-C6H4F)(PPh3)2was prepared from RuCl2(PPh3)3(960 mg, 1.00 mmol) and p-C6H4FCHN2(272 mg, 2.00 mmol, 2.0 eg.). Complex 7 was synthesized in analogy to complex 3. An olive-green microcrystalline solid was obtained. Yield =716 mg (89%). 1H NMR (CD2Cl2): δ19.24 (t, JPH=9.0 Hz, Ru═CH), 7.65-7.62 (m, o-H of C6H4F), 7.50-7.44 and 7.35-7.32 (both m, P(C6H5)3, 6.62 (t, 3JHH=3JHF=8.9 Hz, m-H of C6H4F), 152.21 (s, ipso-C of C6H4F), 134.95 (m, m-C or o-C of P(C6H5)3), 134.04 (d, JCF=19.5 Hz, m-C of C6H4F), 130.56 (s, p-C of P(C6H5)3), 130.08 (d, JCF=8.7 Hz, o-C of C6H4F), 128.47 (m, m-C or o-C of P(C6H5)3, 115.67 (d, JPC=21.8 Hz, ipso-C of P(C6H5)3). 31P NMR (CD2Cl2): δ31.03 (s, PPh3). 19F NMR (CD2Cl2): δ45.63 (s, C6H4F). Anal. Calcd. for C43H35Cl2FP2Ru: C, 64.18; H, 4.38. Found: C, 64.42; H, 4.42.
[0113] Synthesis of RuCl2(═CH-p-C6H4Cl)(PPh3)2(Complex 8)
[0114] In a technique analogous to that used in example 2, RuCl2(═CH-p-C6H4Cl)(PPh3)2was prepared from RuCl2(PPh3)3(350 mg, 0.37 mmol) and p-C6H4ClCHN2(111 mg, 0.73 mmol, 2.0 eq.) A green microcrystalline solid was obtained. Yield =246 mg (82%). 1H NMR (CD2Cl2); δ19.27 (t, JPH=9.2 Hz, Ru═CH), 7.51-7.44, 7.35-7.32 and 6.67-6.63 (all m, C6H4Cl and P(C6H5)3), 6.86 (d ,3JHH=8.8 Hz, m-H of C6H4Cl). 13C NMR (CD2Cl2): δ307.34 (t, JPC=10.6 Hz, Ru═CH), 153.82 (s, ipso-C of C6H4Cl), 134.91 (m, m-C or o-C of P(C6H5)3), 130.58 (s, p-C of P(C6H5)3, 128.87, 128.81 and 127.85 (all s, C6H4Cl), 128.48 (s(br.), m-C or o-C of P(C6H5)3, 115.90 (d, JPC=21.7 Hz, ipso-C of P(C6H5)3). 31p NMR (CD2Cl2): δ30.47 (s, PPh3). Anal. Calcd. for C43H35Cl3P2Ru: C, 62.90; H, 4.30. Found: C, 62.87; H, 4.40.
[0115] Synthesis of RuCl2(═CH-p-C6H4NO2)(PPh3)2(Complex 9)
[0116] In a technique analogous to that used in synthesizing complex 3, RuCl2(═CH-p-C6H4NO2)(PPh3)2, complex 9 was prepared from RuCl2(PPh3)3(604 mg, 0.63 mmol) and p-C6H4NO2CHN2(206 mg, 1.25 mmol, 2.0 eq.) A tan microcrystalline solid was obtained. Yield =398 mg (76%). 1H NMR (CD2Cl2): δ19.47 (t, JPH=10.8 Hz, Ru═CH), 7.88-7.67, 7.38-7.33 and 7.02-6.71 (all m, C6H4NO2and P(C6H5)3. 13C NMR (CD2Cl2): δ313.43 (t, JPC=11.2 Hz, Ru═CH), 158.40 (s, ipso-C of C6H4NO2), 148.11 (s, p-C of C6H4NO2), 135.49 (m, m-C or o-C of P(C6H5)3), 132.21 (s, m-C of C6H4NO2), 130.91 (s, p-C of P(C6H5)3, 130.72 (s, o-C of C6H4NO2), 128.86 (m, m-C or o-C of P(C6H4)3, 116.03 (d, JPC=21.6 Hz, ipso-C of P(C6H5)3). 31P NMR (CD2Cl2): δ32.27 (s, PPh3). Anal. Calcd. for C43H35Cl2NO2P2Ru: C, 62.10; H, 4.24; N, 1.68. Found: C, 62.31; H, 4.66; N, 1.84.
[0117] Synthesis of RuCl2(═CHPh)(PCy3)2(Complex 10)
[0118] A solution of RuCl2(═CHPh)(PPh3)2(242 mg, 0.31 mmol) in CH2Cl2(10 mL) was treated with a solution of tricyclohexylphosphine (190 mg, 0.68 mmol, 2.2 eq.) in CH2Cl2(3 mL) and stirred at RT for 30 min. The solution was filtered, and the solvent was removed under vacuum. The residue was repeatedly washed with acetone or methanol (5 mL portions) and dried in vacuo. A purple microcrystalline solid was obtained. Yield 290 mg (89%). 1H NMR (CD2Cl2): δ20.02 (s, Ru═CH) (s, Ru═CH), 8.44 (d, 3JHH=7.6 Hz, o-H of C6H5), 7.56 (t, 3JHH=7.6 Hz, p—H of C6H5), 7.33 (t, 3JHH=7.6 Hz, m-H of C6H5), 2.62-2.58, 1.77-1.67, 1.46-1.39 and 1.25-1.16 (all m, P(C6H11)3. 13C NMR (CD2Cl2): δ294.72 (s, Ru═CH), 153.17 (s, ipso-C of C6H5), 131.21, 129.49 and 129.27 (all s, C6H5), 32.49 (pseudo—t, Japp=9.1 Hz, ipso-C of P(C6H11)3), 30.04 (s, m-C of P(C6H11)3, 28.24 (pseudo-t, Japp=4.5 Hz, o-C of P(C6H11)3), 26.96 (s, p-C of P(C6H11)3). 31P NMR (CD2Cl2): δ36.61 (s, PCy3). Anal. Calcd. for C43H72Cl2P2Ru: C, 62,76; H, 8.82. Found: C, 62.84; H, 8.71.
[0119] One-pot Synthesis of RuCl2(═CHPh)(PCy3)2(Complex 10)
[0120] A solution of RuCl2(PPh3)3(4.0 g, 4.17 mmol) in CH2Cl2(40 mL) was treated at −78° C. with a −50° C. solution of phenyidiazomethane (986 mg, 8.35 mmol, 2.0 eq.) in pentane (10 mL). Upon addition of the diazo compound, an instantaneous color change from orange-brown to green-brown and vigorous bubbling was observed. After the reaction mixture was stirred at −70° C. to −60° C. for 5-10 min, an ice-cold solution of tricyclohexylphosphine (2.57 g, 9.18 mmol, 2.2 eq.) in CH2Cl2was added via syringe. Accompanied by a color change from brown-green to red, the solution was allowed to warm to RT and stirred for 30 min. The solution was filtered, concentrated to half of the volume and filtrated. Methanol (100 mL) was added to precipitate a purple microcrystalline solid, complex 10, that was filtered off, washed several times with acetone and methanol (10 mL portions), and dried under vacuum for several hours. Yield 3.40 g (99%).
[0121] Synthesis of RuCl2(═CH-p-C6H4NMe2)(PCy3)2(Complex 11)
[0122] Starting with RuCl2(═CH-p-C6H4NMe2)(PPh3)2(316 mg, 0.38 mmol) and tricyclohexylphosphine (235 mg, 0.84 mmol, 2.2 eq.) RuCl2(═CH-p-C6H4NMe2)(PCy3)2was obtained as a green microcrystalline solid in a procedure analogous to that used in synthesizing complex 10. Yield 284 mg (86%). 1H NMR (CD2Cl2): δ18.77 (s, Ru═CH), 8.25-8.14 (s(vbr.), o-H of C6H4NMe2), 6.55 (d, 3JHH=7.2 Hz, m-H of C6H4NMe2), 2.97 (s, N(CH3)2), 2.63-2.61, 1.80-1.67, 1.43-1.41 and 1.21-1.17 (all m, P(C6H11)3). 13C NMR (CD2Cl2): δ286.13 (s(br.); Ru═CH), 151.28 (s; ipso-C of C6H4NMe2), 144.80, 134.85 and 110.50 (all s; C6H4NMe2), 40.30 (s, N(CH3)2, 32.54 (pseudo-t, Japp=8.2 Hz, ipso-C of P(C6H11)3), 30.10 (s, m-C of P(C6H11)3), 28.36 (m, o-C of P(C6H11)3), 27.07 (s, p-C of P(C6H11)3. 31P NMR (CD2Cl2); δ34.94 (s, PCy3). Anal. Calcd. for C45H77Cl2NP2Ru: C, 62.41; H, 8.96; N, 1.62. Found: C, 62.87; H, 9.04; N, 1.50.
[0123] Synthesis of RuCl2(═CH-p-C6H4OMe)(PCy3)2(Complex 12)
[0124] Starting with RuCl2(═CH-p-C6H4OMe)(PPh3)2(171 mg, 0.21 mmol) and tricyclohexylphosphine (130 mg, 0.46 mmol, 2.2 eq.), RuCl2(═CH-p-C6H4OMe)(PCy3)2was obtained as a dark-purple microcrystalline solid, in a technique analogous to that used in synthesizing complex 10. Yield 152 mg (85%). 1H NMR (CD2Cl2): δ19.48 (s, Ru═CH), 8.43 (s(br.), o-H of C6H4OMe), 6.82 (d, 3JHH=8.6 Hz, m=H of C6H4OMe), 3.82 (s, OCH3), 2.64-2.59, 1.78-1.68, 1.46-1.39 and 1.26-1.15 (all m, P(C6H11)3, 13C NMR (CD2Cl2); δ290.90 (s(br.), Ru═CH), 148.34 (s, ipso-C of C6H4OMe), 134.91 132.30 and 128.83 (all s, C6H4OMe), 55.81 (S, OCH3), 32.51 (pseudo-t, Japp=9.1 Hz, ipso-C of P(C6H11)3), 30.06 (S, m-C of P(C6H11)3), 28.28 (pseudo-t, Japp=5.2 Hz, o-C of P(C6H11)3), 27.00 (s, p-C of P(C6H11)3). 31P NMR (CD2Cl2): δ35.83 (s, PCy3). Anal. Calcd. for C44H74Cl2OP2Ru: C, 61.96; H, 8.74. Found: C, 62.36; H, 8.71.
[0125] Synthesis of RuCl2(═CH-p-C6H4Me)(PCy3)2(Complex 13)
[0126] Starting with RuCl2(═CH-p-C6H4Me(PPh3)2(416 mg, 0.52 mmol) and tricyclohexylphosphine (321 mg, 1.14 mmol, 2.2 eq.), RuCl2(═CH-p-C6H4Me)(PCy3)2was obtained as a bright-purple microcrystalline solid, in a technique analogous to that used iin synthesizing complex 10. Yield 385 mg (88%). 1H NMR(CD2Cl2): δ19.80 (s, Ru═CH), d, 3JHH=7.6 Hz, o-H of C6H4Me), 7.13 (d, 3JHH=7.6 Hz, m-H of C6H4Me), 2.08 (s, CH3), 2.62-2.58, 1.77-1.67, 1.43-1.40 and 1.22-1.17 (all m, P(C6H11)3). 13C NMR (CD2Cl2): δ293.86 (t, JPC=8.3 Hz, Ru═CH), 141.48 (s, ipso-C of C6H4Me), 131.56 and 129.85 (both s, C6H4Me), 32.52 (pseudo-t, Japp=9.2 Hz, ipso-C of P(C6H11)3), 30.07 (S, m-C of P(C6H11)3), 28.26 (pseudo-t, Japp=4.1 Hz, o-C of P(C6H11)3), 27.00 (s, p-C of P(C6H11)3), 22.39 (s, CH3). 31P NMR (CD2Cl2): δ36.09 (s, PCy3). Anal. Calcd. for C44H74Cl2P2Ru: C, 63.14; H, 8.91. Found: C, 63.29; H, 8.99.
[0127] Synthesis of RuCl2(═CH-p-C6H4F)(PCy3)2(Complex 14)
[0128] Starting with RuCl2(═CH-p-C6H4F)(PPh3)2(672 mg, 0.84 mmol) and tricyclohexylphosphine (515 mg, 1.84 mmol, 2.2 eq.), RuCl2(═CH-p-C6H4F)(PCy3)2was obtained as a purple microcrystalline solid, in a technique analogous to that used in synthesizing complex 10. Yield 583 mg (83%). 1H NMR (CD2Cl2): δ19.86 (s, Ru═CH), 8.52-8.50 (s(br.), o-H of C6H4F), 7.00 (dd, 3JHH=3JHF=8.8 Hz, m-H of C6H4F), 2.63-2.59, 1.77-1.68, 1.47-1.40 and 1.26-1.17 (all m, P(C6H11)3). 13C NMR(CD2Cl2): δ291.52 (t, JPC=8.6 HZ, Ru═CH), 162.10 (d, JCF=254.3Hz, p-C of C6H4F), 150.57 (S, ipso-C of C6H4F), 134.10 (d, JCF=8.9Hz, o-C of C6H4F), 116.00 (d, jCF=21.3 Hz, m-C of C6H4F), 32.49 (pseudo-t, Japp9.3 Hz, ipso-C of P(C6H11)3), 30.05 (s, m-C of P(C6H11)3), 28.22 (pseudo-t, Japp=5.2 Hz, o-C of P(C6H11)3), 26.94 (s, p-C of P(C6H11)3. 31P NMR(CD2Cl2): δ636.60 (s, PCy3). 19F NMR(CD2Cl2): δ45.47 (s, C6H4F). Anal. Calcd. for C43H71Cl2FP2Ru: C, 61.41; H, 8.51. Found: C, 61.32; H, 8.59.
[0129] Synthesis of RuCl2(═CH-p-C6H4Cl)(PCy3)2(Complex 15)
[0130] Starting with RuCl2(═CH-p-C6H4Cl)(PPh3)2(543 mg, 0.66 mmol) and tricyclohexylphosphine (408 mg, 1.45 mmol, 2.2 eq.), RuCl2(═CH-p-C6H4Cl)(PCy3)2was obtained as a purple microcrystalline solid in a technique analogous to that used in synthesizing complex 10. Yield 493 mg (87%). 1H NMR(CD2Cl2): δ19.98 (s, Ru═CH), 8.43 (d, 3JHH8.7 Hz, o-H of C4H4Cl), 7.29 (d, 3JHH8.7 Hz, m-H of C6H4Cl), 2.63-2.58, 1.76-1.68, 1.46-1.41 and 1.25-1.17 (all m, P(C6H11 )3). 13C NMR(CD2Cl2): δ291.52 (t, JPC8.0 HZ, Ru═CH), 151.81 (s, ipso-C of C6H4Cl), 134.64 (S, p-C of C6H4Cl), 132.56 and 129.51 (both s, o-C and m-C of C6H4Cl), 32.51 (pseudo-t, Japp8.9 Hz, ipso-C of P(C6H11)3), 30.06 (s, m-C of P(C6H11)3), 28.22 (pseudo-t, Japp5.2 Hz, o-C of P(C6H11)3),26.96 (s, p-C of P(C6H11)3). 31P NMR(CD2Cl2): δ36.81 (s, PCy3).Anal. Calcd. for C43H71Cl2FP2Ru: C, 60.24; H, 8.35. Found: C, 60.22; H, 8.45.
[0131] Synthesis of RuCl2(═CH-p-C6H4NO2)(PCy3)2(Complex 16)
[0132] Starting with RuCl2(═CH-p-C6H4NO2)(PPh3)2(609 mg, 0.73 mmol) and tricyclohexylphosphine (452 mg, 1.61 mmol, 2.2 eq.), RuCl2(═CH-p-C6H4NO2)(PCy3)2was obtained, in a procedure analogous to that in example 11, as a red-purple microcrystalline solid. Yield 527 mg (83%). 1H NMR(CD2Cl2): δ20.71 (s, Ru═CH), 8.64 (d, 3JHH8.4 Hz, o-H of C6H4NO2), 8.13 (d, 3JHH=8.4 Hz, m-H of c6h4no2), 2.63-2.58, 1.73-1.68, 1.47-1.40 and 1.26-1.17 (all m, P(C6H11)3). 13C NMR (CD2Cl2) δ289.07 (t, JPC7.6 Hz, Ru═CH), 155.93 (s, ipso-C of C6H4NO2), 145.34 (s, p-C of C6H4NO2), 131.22 and 125.06 (both s, o-C and m-C of C6H4NO2), 32.57 (pseudo-t, Japp=9.2 Hz, ipso-C of P(C6H11)3), 30.05 (s, m-C of P(C6H11)3), 28.16 (pseudo-t, Japp=4.1 Hz, o-C of P(C6H11)3). 31P NMR(CD2Cl2): δ38.11 (s, PCy3). Anal. Calcd. for C43H71Cl2NO2P2Ru: C, 59.50; H, 8.25; N, 1.61. Found: C, 59.18; H, 8.25; N, 1.49.
[0133] One-pot Synthesis of RuCl2(═CHPh)(PCp3)2(complex 17)
[0134] Complex 17 is obtained in analogy to complex 10 as a purple microcrystalline solid, using RuCl2(PPh3)3(4.00 g, 4.17 mmol), phenyidiazomethane (986 mg, 8.35 mmol, 2.0 eq.), and tricyclopentyl-phosphine (2.19 g, 9.18 mmol, 2.2. eq.). Due to the better solubility of 17, only methanol is used for the washings. Yield 2.83 g (92%). 1H NMR (CD2Cl2): δ20.20 (s, Ru═CH), 8.47 (d, 3JHH=7.5 Hz, o-H of C6H5), 7.63 (t, 3JHH=7.5 Hz, p-H of C6H5), 7.36 (t, 3JHH=7.5 Hz, m-H of C6H5), 2.68-2.62, 1,81-1.77, 1.62-1.52 and 1.49-1.44 (all m, P(C5H9)3). 13C NMR (CD2Cl2): δ300.52 (t,JPC=7.6 Hz, Ru═CH), 153.38 (s, ipso-C of C6H5), 130.99, 129.80 and 129.53 (all s, C6H5) 35.54 (pseudo-t, Japp=11.2 Hz, ipso-C of P(C5H9)3) 29.99 and 26.39 (both s, P(C5H9)3). 13P NMR (CD2Cl2): δ29.96 (s, PCp3). Anal. Calcd. for C37H60Cl2P2Ru: 60.15; H, 8.19. Found: C, 60.39; H, 8.21.
[0135] One-pot Synthesis of RuCl2(═CHPh)(PiPr3)2(complex 18)
[0136] Complex 18 is obtained in analogy to complex 17 as a purple microcrystalline solid, using RuCl2(PPh3)3(4.00 g, 4.17 mmol), phenyldiazomethane (986 mg, 8.35 mmol, 2.0 eq.), and triisopropylphosphine (1.79 mL, 9.18 mmol, 2.2. eq.). Yield 2.26 g (93%). 1H NMR (CD2Cl2): δ20.10 (s, Ru═CH), 8.52 (d, 3JHH=7.6 Hz, o-H of C6H5), 7.36 (t, 3JHH=7.6 Hz, p-H of C6H5), 7.17 (t, 3JHH=7.6 Hz, m-H of C6H5), 2.88-2.85, (m, PCHCH3); 1.19 (dvt, N=13.6 Hz, PCHCH3). 13C NMR (CD2Cl2): δ296.84 (s(br.), Ru═CH), 152.81 (s, ipso-C of C6H5), 131.37, 129.54 and 129.20 (all s, C6H5) 22.99 (vt, N=2JPC+4JPC=18.9 Hz, PCHCH3), 19.71 (s, PCHCH3). 13P NMR (CD2Cl2): δ45.63 (s, PiPr3). Anal. Calcd. for C25H48Cl2P2Ru: C, 51.54; H, 8.31. Found: C, 51.69; H, 8.19.
[0137] Synthesis of RuCl2(═CH2)(PCy3)2(Complex 19)
[0138] A solution of RuCl2(═CHPh)(PCy3)2(821 mg, 1.00 mmol) in CH2Cl2(15 mL) was stirred under an atmosphere of ethylene for 15 min at RT. The solvent was removed under vacuum, the residue repeatedly washed with acetone or pentane (5 mL) and dried under vacuum for several hours. A burgundy microcrystalline solid was obtained. Yield 745 mg (quant.). 1H NMR (CD2Cl2): δ18.94 (s, Ru═CH2), 2.50-2.44, 1.81-1.70, 1.49-1.43 and 1.25-1.23 (all m, P(C6H11)3). 13C NMR (CD2Cl2): δ294.71 (t, JPC=7.6 Hz, JCH=164.0 Hz (gated decoupled), Ru═CH), 31.05(pseudo-t, Japp=9.6 Hz, ipso-C of P(C6H11)3), 29.58 (s, m-C of P(C6H11)3), 28.20 (pseudo-t, Japp=5.3 Hz, o-C of P(C6H11)3), 26.94 (s, p-C of P(C6H11)3). 31P NMR (CD2Cl2): δ43.74 (s, PCy3). Anal. Calcd. for C37H68Cl2P2Ru: C, 59.50; H, 9.18. Found: C, 59.42; H, 9.29.
[0139] Synthesis of RuCl2(═CHMe)(PCy3)2(Complex 20)
[0140] In a procedure analogous to that used in synthesizing complex 19, RuCl2(═CHMe)(PCy3)2was obtained as a red-purple microcrystalline solid, using RuCl2(═CHPh)(PCy3)2(763 mg, 0.93 mmol) and propylene (or 2-butene) as starting materials. Yield 691 mg (98%). 1H NMR (CD2Cl2): δ19.26 (q, 3JHH=5.1 Hz, Ru═CH), 2.57 (d, 3JHH=5.1 Hz, CH3), 2.59-2.53, 1.87-1.79, 1.57-1.50 and 1.28-1.23 (all m, P(C6H11)3). 3C NMR (CD2Cl2): δ316.32 (t, JPC=7.6 Hz, Ru═CH), 49.15 (s, CH3), 32.37 (pseudo-t, Japp=9.4 Hz, ipso-C of P(C6H11)3), 29.87 (s, m-C of P(C6H11)3), 28.22 (pseudo-t, Japp=5.0 Hz, o-C of P(C6H11)3), 26.94 (s, p-C of P(C6H11)3). 31P NMR (CD2Cl2): δ35.54 (s, PCy3). Anal. Calcd. for C38H70Cl2P2Ru: C, 59.58; H, 9.27. Found: C, 59.91; H, 9.33.
[0141] Synthesis of RuCl2(═CHEt)(PCy3)2(Complex 21)
[0142] In a procedure analogous to that used in synthesizing complex 19, RuCl2(═CHEt)(PCy3)2was obtained as a red-purple microcrystalline solid, using RuCl2(═CHPh)(PCy3)2and a tenfold excess of 1-butene (or cis-3-hexene) as starting materials. Yield 616 mg (97%). 1H NMR (CD2Cl2): δ19.12 (t, 3JHH=5.0 Hz, Ru═CH), 2.79 (dq,3JHH=5.0, 3JHH′=7.1 Hz, CH2CH3), 2.55-2.49, 1.84-1.81, 1.54-1.47 and 1.26-1.23 (all m, P(C6H11)3), 1.35 (t, 3JHH′=7.1 Hz, CH2CH3). 13C NMR (CD2Cl2): δ322.59 (t, JPC=9.3 Hz, Ru═CH), 53.48 (s, CH2CH3), 32.20 (pseudo-t, Japp=8.9 Hz, ipso-C of P(C6H11)3), 29.85 (s, m-C of P(C6H11)3, 29.57 (s, CH2CH3), 28.22 (pseudo-t, Japp=4.6 Hz, o-C of P(C6H11)3), 26.88 (s, p-C of P(C6H11)3). 31P NMR (CD2Cl2): δ36.39 (s, PCy3). Anal. Calcd. for C39H72Cl2P2Ru: C, 60.45; H, 9.37. Found: C, 60.56; H, 9.30.
[0143] Synthesis of RuCl2(═CH—n—Bu)(PCy3)2(Complex 22)
[0144] In a procedure analogous to that used in synthesizing complex 19, RuCl2(═CH—n—Bu)(PCy3)2was obtained as a red-purple microcrystalline solid, using RuCl2(═CHPh)(PCy3)2(354 mg, 0.43 mmol) and 1-hexene (538 μL, 4.30 mmol, 10 eq.) as starting materials. Yield 328 mg (95%). 1H NMR (CD2Cl2); δ19.24 (t, 3JHH=5.1 Hz, Ru═CH), 2.74 (dt, 3JHH=5.1, 3JHH′=5.2 Hz, (CHCH2), 2.56-2.47, 1.82-1.78, 1.70-1.68, 1.54-1.43, 1.26-1.22 and 0.95-0.86 (all m, CH2CH2CH3and P(C6H11)3). 13C NMR (CD2Cl2): δ321.13 (t, JPC=7.6 Hz, Ru═CH), 58.85 (s, CHCH2) 32.25 (pseudo-t, Japp=9.4 Hz, ipso-C of P(C6H11)3), 29.90 (S, m-C of P(C6H11)3), 28.23 (pseudo-t, Japp=5.3 Hz, o-C of P(C6H11)3, 26.91 (s, p-C of P(C6H11)3), 30.53, 22.94 and 14.06 (all s, CH2CH2CH3). 31P NMR (CD2Cl2): δ36.05 (s, PCY3). Anal. Calcd. for C41H76Cl2P2Ru: C, 61.32; H, 9.54. Found: C, 61.51; H, 9.71.
[0145] Synthesis of RuCl2(═CHCH═CH2)(PCy3)2 (Complex 23)
[0146] 1,3-butadiene is slowly bubbled into a solution of complex 10 (703 mg, 0.85 mmol) in CH2Cl2(15 mL) for 20 seconds at −20° C. While the solution is allowed to warm to RT within 10 min, a color change from purple to orange-brown is observed. The solvent was removed under vacuum, the residue repeatedly washed with acetone or pentane (5 mL) and dried under vacuum for several hours. A red-purple microcrystalline solid was obtained. Yield 627 mg (95%). 1H NMR (CD2Cl2): δ19.06 (d, 3JHH=10.5 Hz, Ru═CH), 8.11 (ddd, 3JHH10.5, 3JHHcis=9.3, 3JHHtrans=16.8 Hz, CH═CH2), 6.25 (d, 3JHHcis=9.3, Hcisof CH═CH2), 6.01 (d, 3JHHtrans=9.3, Htransof CH═CH2), 2.59-2.53, 1.83-1.78, 1.52-1.47 and 1.25-1.21 (all m, P(C6H11)3). 13C NMR (CD2Cl2): δ296.00 (t, JPC7.6 Hz. Ru═CH), 153.61 (s, CH═CH2), 115.93 (s, CH═CH2), 32.32 (pseudo-t, Japp=8.9 Hz, ipso-C of P(C6H11)3), 29.82 (s, m-C of P(C6H11)3), 28.15 (pseudo-t, Japp=5.1 Hz, o-C of P(C6H11)3), 26.91 (s, p-C of P(C6H11)3). 31P NMR (CD2Cl2): δ36.17 (s, PCy3). Anal. Calcd. for C39H70Cl2P2Ru: C, 60.61; H, 9.13. Found: C, 60.79; H, 9.30.
[0147] Synthesis of RuCl2(═C═CH2)(PCy3)2(Complex 24)
[0148] In a procedure analogous to that used in synthesizing complex 23, RuCl2(═C═CH2)(PCy3)2was obtained as a tan microcrystalline solid, using complex 10 (413 mg, 0.50 mmol) and 1,2-propadiene as starting materials. Yield 373 mg (98%). 1H NMR (CD2Cl2): δ3.63 (s, Ru═C═CH2), 2.71-2.64, 2.05-2.01, 1.81-1.53 and 1.32-1.23 (all m, P(C6H11)3. 13C NMR (CD2Cl2): δ327.41 (t, JPC=17.2 Hz, Ru═C═CH2), 99.34 (s, Ru═C═CH2), 33.30 (pseudo=t, Japp=8.9 Hz, ipso-C of P(C6H11)3), 30.41 (s, m-C of P(C6H11)3), 28.32 (pseudo-t, Japp=5.0 Hz, o-C of P(C6H11,)3), 27.02 (s, p-C of P(C6H11)3). 31P NMR (CD2Cl2): δ35.36 (s, PCy3). Anal. Calcd. for C38H68Cl2P2Ru: C, 60.14; H, 9.03. Found: C, 60.29; H, 8.91.
[0149] Synthesis of RuCl2(═CHCH2OAc)(PCy3)2(Complex 25)
[0150] A solution of complex 10 (423 mg, 0.51 mmol) in CH2Cl2(10 mL) was treated with allyl acetate (555 μL, 5.10 mmol, 10 eq.) at −20° C. While the solution warmed to RT within 10 min, a color change from purple to orange-brown was observed. The solvent was removed under vacuum, the residue repeatedly washed with ice-cold methanol (5 mL portions) and dried under vacuum for several hours. A purple microcrystalline solid, RuCl2(═CHCH2OAc)(PCy3)2, was obtained. Yield 342 mg (83%). 1H NMR (CD2Cl2): δ18.90 (t, 3JHH=4.2 Hz, Ru═CH), 4.77 (d, 3JHH=3.6 Hz, CH2OAc), 2.09 (s, C(O)CH3), 2.53-2.47, 1.81-1.70, 1.59-1.53 and 1.26-1.22, (all m, P(C6H11)3). 13C NMR (CD2Cl2): δ305.76 (t, JPC=7.6 Hz, Ru═C), 170.41 (s. C(O)CH3), 83.19 (s, CH2OAc), 32.59 (pseudo-t, Japp=8.6 Hz, ipso-C of P(C6H11)3), 29.94 (s, m-C of P(C6H11)3), 28.23 (m, o-C of P(C6H11)3), 26.91 (s. p-C of P(C6H11)3), 20.91 (s, C(O)CH3). 31P NMR (CD2Cl2): δ36.66 (s, PCy3). Anal. Calcd. for C39H72Cl2O2P2Ru: C, 58.05; H, 8.99. Found: C, 58.13; H, 9.07.
[0151] Synthesis of RuCl2(═CHCH2Cl)(PCy3)2(Complex 26)
[0152] In a procedure analogous to that used in synthesizing complex 25 RuCl2(═CHCH2Cl)(PCy3)2was obtained as a purple microcrystalline solid using complex 10 (583 mg, 0.71 mmol) and allyl chloride (577 μL, 7.08 mmol, 10 eq.) as starting materials. Yield 552 mg (80%). 1H NMR(CD2Cl2): δ18.74 (t, 3JHH=4.5 Hz, Ru═CH), 4.43(d, 3JHH4.8 Hz, CH2Cl), 2.55-2.50, 1.81-1.70, 1.59-1.52 and 1.27-1.23 (all m, P(C6H11)3). 13C NMR(CD2Cl2): δ303.00 (t, JPC=7.8 Hz, Ru═C), 63.23 (s, CH2Cl), 32.05(pseudo-t, Japp=8.8 Hz, ipso-C of P(C6H11)3), 29.50(s, m-C of P(C6H11,)3), 27.81 (pseudo-t, Japp=5.2 Hz, o-C of P(C6H11)3), 26.56(s, p-C of P(C6H11)3). 31P NMR(CD2Cl2): δ37.36 (s, PCy3). Anal. Calcd. for C38H69Cl3P2Ru: C, 57.39; H, 8.74. Found: C, 57.55; H, 8.81.
[0153] Synthesis of RuCl2(═CH(CH2)3OH)(PCy3)2(Complex 27)
[0154] In a procedure analogous to that used in synthesizing complex 25, RuCl2(═CH(CH2)3OH)(PCy3)2was obtained as a purple microcrystalline solid, using complex 10 (617 mg, 0.82 mmol) and 4-pentene-1-ol (823 μL, 8.2 mmol, 10 eq.) as starting materials. Yield 459 mg (76%). 1H NMR(CD2Cl2): δ19.20 (t, 3JHH=4.6 Hz, Ru═CH, 5.46(s(br.), OH), 2.82-2.78, 2.06-2.01 and 1.62-1.58 (all m, CH2CH2CH2OH), 2.55-2.51, 1.84-1.81, 1.55-1.52 and 1.26-1.23 (all m, P(C6H11)3). 13C NMR(CD2Cl2): δ305.66 5, JPC=7.3 Hz, Ru═C, 62.66 (s, CH2OH), 33.01 and 30.08 (both s, CH2CH2) 32.32(pseudo-t, Japp=8.5 Hz, ipso-C of P(C6H11)3), 29.94 (s, m-C of P(C6H11)3), 28.28. (pseudo-t, Japp=5.3 Hz, o-C of P(C6H11)3), 26.91 (s, p-C of P(C6H11)3). 31p NMR(CD2Cl2): δ37.06 (s, PCy3). Anal. Calcd. for C40H74Cl2P2ORu: C, 59.69; H, 9.27. Found: C, 59.51; H, 9.09.
[0155] ROMP of Norbornene with Complexes 3-9 as Catalysts
[0156] Norbornene (59 mg, 0.63 mmol) was dissolved in CH2Cl2(0.7 mL) and treated with solutions of complexes 3-9 (6.25 μmol) in CH2Cl2(0.3 mL) at RT. The reaction mixtures became viscous within 3-5 min and the color changed from brown-green to orange. The solutions were stirred at RT for 1 hour, then exposed to air and treated with CH2Cl2(2 mL) containing traces of 2,6-di-tert-butyl-4-methylphenol and ethyl vinyl ether. The resulting green solutions were stirred for 20 min and, after filtration through short columns of silica gel, precipitated into vigorously stirred methanol. White, tacky polymers were obtained that were isolated, washed several times with methanol and dried under vacuum. Yields 95-99%, ≈90% trans, Mn=31.5-42.3 kg/mol, PDI (toluene): 1.04-1.10.
[0157] Determination of Initiation and Propagation Rates in ROMP of Norbornene with Complexes 3-9
[0158] 1.25×10−5mol of catalysts based on complexes 3-9 were weighed into NMR tubes and dissolved in benzene-d6(0.3 mL). Ferrocene stock solution in benzene-d6(20 μL) was added as an internal standard. These mixtures were treated with solutions of norbornene (23.5 mg, 0.25 mmol, 20 eq.) in benzene-d6(250 μL). A 1H NMR-routine was started immediately, taking 60 spectra within 40 min, then 200 spectra within 5 hour. The initiation rate constants (ki) were determined by integration of Hα resonances of the initiating and propagating species. The propagation rate constants (kp) were determined by monitoring the decrease of monomer concentration versus the internal standards. The results are given in Table III (above).
[0159] Reaction of Complex 10 with 3-methyl-1-butene and 3,3-dimethyl-1-butene
[0160] In individual NMR-tubes, a solution of complex 10 (5.0 mg, 6.1 μmol) in methylene chloride-d2(0.5 mL) was treated with 10 equiv. 3-methyl-1-butene and 3,3-dimethyl-1-butene (61.0μmol), respectively. Whereas with the latter reactant, no reaction was observed within 12 hours, a gradual (within 5 min) color change from red-purple to orange indicates that complex 10 undergoes a reaction with 3-methyl-1-butene. Resonances in the 1H NMR at δ18.96 (d, 3JHH=7.5 Hz, Ru═CHiPr), 2.27 (m, CHCH3) and 1.01 (d, 3JHH=7.2 Hz, CHCH3) may be attributed to the formation of RuCl2(═CH-i-Pr)(PCy3)2. However, the intensity of these signals did not increase in the course of the reaction, and after 10 min, the corresponding resonances of complex 19 became dominant.
[0161] ROMP of cyclooctene and 1,5-cyclooctadiene with Complexes 10-16 as Catalysts
[0162] Complexes 10-16 (6.0 μmol) were individually dissolved in CH2Cl2(0.5 mL) and treated with neat cyclooctene or 1,5-cyclooctadiene (3.0 mmol, 500 eq.) at RT. Accompanied by a color change from purple to orange, the reaction mixtures turned viscous within 3-5 min. The solutions were stirred at RT for 2.5 hour and, upon exposure to air, treated with CH2Cl2(5 mL) containing traces of 2,6-di-tert-butyl-4-methylphenol and ethyl vinyl ether. After 20 min, the viscous solutions were filtered through short columns of silica gel and precipitated into vigorously stirred methanol. The resulting polymers were isolated, washed several times with methanol and dried under vacuum. Cycloocteneamer (white tacky polymers): Yields 95-100%, Mn=111-211 kg/mol, PDI (toluene): 1.51-1.63; polybutadiene: (white glue-like polymers): Yields 96-99%, 56-68% cis, Mn57.9-63.2 kg/mol, PDI (toluene): 1.56-1.67.
[0163] Determination of Initiation Rate Constants In Acyclic Metathesis of 1-hexene with Complexes 10-16 as Catalysts
[0164] 6.05 μmol of catalysts based on complexes 10-16 were placed into NMR tubes and dissolved in methylene chloride-d2(550 μL). At 0° C., 1-hexene (22.7 μL, 0.18 mmol, 30 eq.) was added and a 1H NMR-routine (at 0° C.) was started, taking 60 spectra within 40 min. The initiation rate constants were determined by integration of the Haresonances of complexes 10-16 and 22. The results are given in Table IV (above).
[0165] X-ray Diffraction Study of RuCl2(═CH-p-C6H4Cl)(PCy3)2(Complex 15)
[0166] A maroon prism of complex 15 was obtained by slow diffusion of hexanes into a concentrated solution of complex 15 in methylene chloride (0.5 mL) within 24 hours. A crystal of the size 0.2mm×0.3mm×0.5 mm was selected, oil-mounted on a glass fiber and transferred to a Siemens P4 diffractometer equipped with a modified LT-1 low temperature system. The determination of Laue symmetry, crystal class, unit cell parameters, and the crystal's orientation matrix were carried out according to standard techniques. Low temperature (158 K) intensity data were collected via a 2θ-θscan technique with MoKα, radiation.
[0167] All 7782 data were corrected for absorption and for Lorentz and polarization effects and placed on an approximately absolute scale. Any reflection with l(net)<0 was assigned the value |Fo|=0. There were no systematic extinctions nor any diffraction symmetry other than the Friedel condition. Refinement of the model proved the centrosymmetric triclinic space group P1 to be the correct choice.
[0168] All crystallographic calculations were carried out using either the UCLA Crystallographic Computing Package or the SHELXTL PLUS program. The analytical scattering factors for neutral atoms were used throughout the analysis; both the real (Δf′) and imaginary (iΔf″) components of anomalous dispersion were included. The quantity minimized during least-squares analysis was Σx(|Fo|−Fc|2where w−1=σ2(|Fo|)+0.0002(|Fo|)2. The structure was solved by direct methods (SHELXTL) and refined by full-matrix least-squares techniques. Hydrogen atoms were located from a difference-Fourier map and included with isotropic temperature parameters. Refinement of the model led to convergence with RF=3.5%, RwF=3.6% and GOF=1.42 for 726 variables refined against those 6411 data with |Fo|>3.0σ(|Fo|)). A final difference-Fourier map yielded ρmax =0.52 eÅ−3.
Claims
Certificate of Correction present
The claims shown below may not include correction changes. Use the corrected PDF for authoritative text.
What is claimed is:
1. A process for polymerizing cyclic olefins comprising the step of contacting a cyclic olefin with a compound of the formula
wherein:
M is selected from the group consisting of Os and Ru;
R1is hydrogen;
R is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;
X and X1are independently selected from any anionic ligand; and
L and L1are independently selected from any neutral electron donor.
2. The process of claim 1, wherein the substituted alkyl includes one or more moieties selected from the group consisting of aryl, alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen.
3. The process of claim 1, wherein the substituted aryl includes one or more moieties selected from the group consisting of alkyl, aryl, alcohol, thiol, ketone, aldehyde, ester, ether, amine, imine, amide, nitro, carboxylic acid, disulfide, carbonate, isocyanate, carbodiimide, carboalkoxy, and halogen.
4. The process of claim 1, wherein R is selected from the group consisting of
(a) hydrogen;
(b) C1-C20alkyl;
(c) aryl;
(d) C1-C20alkyl substituted with one or more moieties selected from the group consisting of aryl, halide, hydroxy, C1-C20alkoxy, and C2-C20alkoxycarbonyl; and
(e) aryl substituted with one or more moieties selected from the group consisting of C1-C20alkyl, aryl, hydroxyl, C1-C5alkoxy, amino, nitro, and halide.
5. The process of claim 4 wherein R is phenyl or phenyl substituted with a moiety selected from the group consisting of chloride, bromide, iodide, fluoride, —NO2, —NMe2, methoxy, and methyl.
6. The process of claim 5 wherein R is phenyl.
7. The process of claim 4 wherein R is selected from the group consisting of hydrogen, methyl, ethyl, n-butyl, iso-propyl, —CH2Cl, —CH2CH2CH2OH, and —CH2OAc.
8. The process of claim 1 wherein L and L1are independently selected from the group consisting of phosphine, sulfonated phosphine, phosphite, phosphinite, phosphonite, arsine, stibine, carbene, ether, amine, amide, sulfoxide, carboxyl, nitrosyl, pyridine, and thioether.
9. The process of claim 1 wherein L and L1are phosphines independently selected from PR3R4R5wherein R3is selected from the group consisting of secondary alkyl and cycloalkyl and wherein R4and R5are independently selected from the group consisting of aryl, C1-C10primary alkyl, secondary alkyl, and cycloalkyl.
10. The process of claim 9 wherein L and L1are independently selected from the group consisting of —P(cyclohexyl)3, —P(cyclopentyl)3, and —P(isopropyl)3.
11. The process of claim 8 wherein L and L1are both —P(phenyl)3.
12. The process of claim 8 wherein L and L1are the same.
13. The process of claim 1 wherein X and X1are independently selected from the group consisting of halogen, hydrogen, unsubstituted moiety, and a substituted moiety wherein the moiety is selected from a group consisting of C1-C20alkyl, aryl, C1-C20alkoxide, aryloxide, C3-C20alkyldiketonate, aryldiketonate, C1-C20carboxylate, arylsulfonate, C1-C20alkylsulfonate, C1-C20alkylthio, C1-C20alkylsulfonyl, and C1-C20alkylsulfinyl, wherein the moiety substitution is selected from a group consisting of C1-C5alkyl, halogen, C1-C5alkoxy, unmodified phenyl, halogen substituted phenyl, C1-C5alkyl substituted phenyl, and a C1-C5alkoxy substituted phenyl.
14. The process of claim 1 wherein X and X1are independently selected from Cl, Br, I, H, unsubstituted moiety, and substituted moiety wherein the moiety is selected from a group consisting of benzoate, C1-C5carboxylate, C1-C5alkyl, phenoxy, C1-C5alkoxy, C1-C5alkylthio, arylsulfonate, and C1-C5alkyl sulfonate wherein the moiety substitution is selected from a group consisting of C1-C5alkyl, unmodified phenyl, halogen substituted phenyl, C1-C5alkyl substituted phenyl, and C1-C5alkoxy substituted phenyl.
15. The process of claim 14 wherein X and X1are independently selected from the group consisting of Cl, CF3CO2, CH3CO2, CFH2CO2, (CH3)3CO, (CF3)2(CH3)CO, (CF3)(CH3)2CO, PhO, MeO, EtO, tosylate, mesylate, and trifluoromethanesulfonate.
16. The process of claim 15 wherein X and X1are both Cl.
17. The process of claim 1 wherein the cyclic olefin is synthesized by a process comprising the step of contacting a diene with a compound of the formula
wherein:
M′ is selected from the group consisting of Os and Ru;
R6is hydrogen;
R7is selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;
X2and X3are independently selected from any anionic ligand; and
L2and L3are independently selected from any neutral electron donor.
18. The process of claim 17 wherein
M′ is selected from the group consisting of Os and Ru;
R6is hydrogen;
R7is a group selected from the group consisting of
(a) hydrogen;
(b) C1-C4alkyl;
(c) phenyl;
(d) C1-C4alkyl substituted with one or more moieties selected from the group consisting of halide, hydroxy, and C2-C5alkoxycarbonyl; and
(e) phenyl substituted with one or more moieties selected from the group consisting of C1-C5alkyl, C1-C5alkoxy, amino, nitro, and halide;
X2and X3are independently selected from any anionic ligand; and
L2and L3are independently phosphines of the formula PR3R4R5wherein R3is selected from the group consisting of secondary alkyl and cycloalkyl and wherein R4and R5are independently selected from aryl, C1-C10primary alkyl, secondary alkyl and cycloalkyl.
19. The process of claim 18, wherein R7is phenyl, M′ is Ru, X2and X3are both Cl, and L2and L3are the same and are selected from the group consisting of —P(cyclohexyl)3, —P(cyclopentyl)3, and —P(isopropyl)3.
21. The process of claim 20 wherein
M is selected from the group consisting of Os and Ru;
R1is hydrogen;
R is a group selected from the group consisting of
(a) hydrogen;
(b) C1-C4alkyl;
(c) phenyl;
(d) C1-C4alkyl substituted with one or more moieties selected from the group consisting of halide, hydroxy, and C2-C5alkoxycarbonyl; and
(e) phenyl substituted with one or more moieties selected from the group consisting of C1-C5alkyl, C1-C5alkoxy, amino, nitro, and halide;
X and X1are independently selected from any anionic ligand; and
L and L1are independently phosphines of the formula PR3R4R5wherein R3is selected from the group consisting of secondary alkyl and cycloalkyl and wherein R4and R5are independently selected from aryl, C1-C10primary alkyl, secondary alkyl and cycloalkyl.
22. The process of claim 21 wherein R is phenyl, M is Ru, X and X1are both Cl, and L and L1are the same and are selected from the group consisting of —P(cyclohexyl)3, —P(cyclopentyl)3, and —P(isopropyl)3.
23. The process of claim 1 wherein L is carbene and L1is selected from the group consisting of —P(cyclohexyl)3, —P(cyclopentyl)3, and —P(isopropyl)3.
24. A process for polymerizing cyclic olefins comprising the step of contacting a cyclic olefin with a compound of the formula
wherein:
M is selected from the group consisting of Os and Ru;
R and R1are the same or different and are each independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;
X and X1are independently selected from any anionic ligand;
L is selected from any neutral electron donor; and
L1is a phosphine of the formula PR3R4R5wherein R3is selected from the group consisting of secondary alkyl and cycloalkyl and wherein R4and R5are independently selected from the group consisting of aryl, C1-C10primary alkyl, secondary alkyl, and cycloalkyl.
25. A process for synthesizing a compound of the formula
comprising the step of contacting a compound of the formula
with an olefin of the formula
wherein:
M is selected from the group consisting of Os and Ru;
R and R1are the same or different and are each independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;
R11and R12are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;
X and X1are independently selected from any anionic ligand;
L is selected from any neutral electron donor; and
L1is a phosphine of the formula PR3R4R5wherein R3is selected from the group consisting of secondary alkyl and cycloalkyl and wherein R4and R5are independently selected from the group consisting of aryl, C1-C10primary alkyl, secondary alkyl, and cycloalkyl.
26. A process for synthesizing a compound of the formula
comprising the step of contacting a compound of the formula (XX1MLnL1m)pwith a diazo compound of the formula RC(N2)R1in the presence of a neutral electron donor of the formula L2wherein:
M is selected from the group consisting of Os and Ru;
R and R1are independently selected from the group consisting of hydrogen, substituted or unsubstituted alkyl, and substituted or unsubstituted aryl;
X and X1are independently selected from any anionic ligand;
L and L2are independently selected from any neutral electron donor;
L1is a phosphine of the formula PR3R4R5wherein R3is selected from the group consisting of secondary alkyl and cycloalkyl and wherein R4and R5are independently selected from the group consisting of aryl, C1-C10primary alkyl, secondary alkyl, and cycloalkyl;
n and m are independently 0-3, provided n+m=3; and
p is an integer greater than 0.
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