Synthesis, Reactivity, and Catalytic Activity of Triangular ZrM2 (M = Rh, Ir) Early-Late Heterobimetallic Complexes
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- 作者：Marc A. F. Hernandez-Gruel ; Jesú ; s J. Pé ; rez-Torrente ; Miguel A. Ciriano ; Angel B. Rivas ; Fernando J. Lahoz ; Isabel T. Dobrinovitch ; and Luis A. Oro
- 刊名：Organometallics
- 出版年：2003
- 出版时间：March 17, 2003
- 年：2003
- 卷：22
- 期：6
- 页码：1237 - 1249
- 全文大小：253K
- 年卷期：v.22,no.6(March 17, 2003)
- ISSN：1520-6041
文摘
Reactions of the zirconium-sulfide metallocene anion [Cptt2ZrS2]2- (Cptt = 
images/gifchars/eta.gif" BORDER=0 >5-1,3-di-tert-butylcyclopentadienyl) with [{M(images/entities/mgr.gif">-Cl)(diolefin)}2 gave the d0-d8 complexes [Cptt2Zr(images/entities/mgr.gif">3-S)2{M(diolefin)}2] (M = Rh, diolefin = 2,5-norbornadiene (nbd) (1), 1,5-cyclooctadiene (cod); M= Ir, diolefin = cod) with a triangular ZrM2 core capped by two symmetrical images/entities/mgr.gif">3-sulfido ligands.The rhodium complexes [Cptt2Zr(images/entities/mgr.gif">3-S)2{Rh(diolefin)}2] (diolefin = tetrafluorobenzobarrelene(tfbb), nbd, cod) can also be prepared by the additive-deprotonation reactions of themononuclear [Rh(acac)(diolefin)] (diolefin = nbd, tfbb) and the dinuclear [{Rh(images/entities/mgr.gif">-OH)(cod)}2]complexes with [Cptt2Zr(SH)2]. These compounds exist as two rotamers in solution due to ahindered rotation of the cyclopentadienyl rings and the relative disposition of the substituentsof the Cptt groups in the sandwich moiety. The reaction of [Cptt2Zr(SH)2] with [Ir(acac)(cod)]gave the complex [Cptt(acac)Zr(images/entities/mgr.gif">3-S)2{Ir(cod)}2] (5) with release of HCptt and coordination ofacetylacetonate to the zirconium center. Carbonylation of compounds 1 and 5 yielded [Cptt2Zr(images/entities/mgr.gif">3-S)2{Rh(CO)2}2] (6) and [Cptt(acac)Zr(images/entities/mgr.gif">3-S)2{Ir(CO)2}2], respectively, while the complexes[Cptt2Zr(images/entities/mgr.gif">3-S)2{M(CO)2}2] (M = Rh, Ir) resulted also from the reaction of [Cptt2Zr(SH)2] with(PPh3Bz)[MCl2(CO)2] in the presence of triethylamine. Reactions of the carbonyl complexeswith 1 molar equiv of bis(diphenylphosphino)methane (dppm) gave the cisoid complexes [Cptt2Zr(images/entities/mgr.gif">3-S)2{M(CO)}2(images/entities/mgr.gif">-dppm)] (M = Rh (9), Ir) with evolution of carbon monoxide. Monodentatephosphites, P(OMe)3 and P(OPh)3, react with 6 to give mixtures of the transoid and cisoidisomers [Cptt2Zr(images/entities/mgr.gif">3-S)2{Rh(CO)(P(OR)3)}2], which also exhibit a restricted rotation of the Cpttrings. The molecular structures of complexes 6 and 9 have been determined by X-raydiffraction methods. Compound 6 in the presence of P-donor ligands, P(OMe)3, P(OPh)3, andPPh3, is a precursor of the catalyst for the hydroformylation of oct-1-ene under mild conditionsof pressure and temperature. No Zr-Rh synergic effect is observed in this case, and theprecursor breaks down after catalysis.