The Anions [Cptt2Zr(-S)2M(CO)2]- (M = Rh, Ir) as Versatile Precursors for the Synthesis of Sulfido-Bridged Early-Late Heterotrimetallic (ELHT) Co
详细信息 查看全文
- 作者：Marc A. F. Hernandez-Gruel ; Isabel T. Dobrinovitch ; Fernando J. Lahoz ; Luis A. Oro ; Jesú ; s J. Pé ; rez-Torrente
- 刊名：Organometallics
- 出版年：2007
- 出版时间：December 3, 2007
- 年：2007
- 卷：26
- 期：25
- 页码：6437 - 6446
- 全文大小：412K
- 年卷期：v.26,no.25(December 3, 2007)
- ISSN：1520-6041
文摘
The reaction of [Cptt2Zr(3-S)2{Ir(CO)2}2] (Cptt = 5-1,3-di-tert-butylcyclopentadienyl) with dppe (1,2-bis-(diphenylphosphino)ethane) affords the ion-pair compound [Ir(CO)(dppe)2][Cptt2Zr(-S)2Ir(CO)2] (2).The related compound [Rh(dppe)2][Cptt2Zr(-S)2Rh(CO)2] (5) has been obtained in solution under a carbonmonoxide atmosphere by reaction of [Cptt2Zr(3-S)2{Rh(CO)2}2] with dppe through the intermediateheterotrinuclear compound [Cptt2Zr(3-S)2{Rh(dppe)}{Rh(CO)2}] (4). Reaction of the heterodinuclearanion [Cptt2Zr(-S)2Ir(CO)2]-, generated in situ, with [Rh(-Cl)(cod)]2, [RhCl2(CO)2]- and [Pd(-Cl)(3-C3H5)]2 affords the d0-d8-d8 early-late compounds [Cptt2Zr(3-S)2{Ir(CO)2}{Rh(cod)}] (6), [Cptt2Zr(3-S)2{Ir(CO)2}{Rh(CO)2}] (7), and [Cptt2Zr(3-S)2{Ir(CO)2}{Pd(3-C3H5)}] (8) each with a symmetrical trigonal-bipyramidal M3(3-S)2 heterotrimetallic metal-sulfur core. In the same way, the reactionof [Cptt2Zr(-S)2M(CO)2]- (M = Rh, Ir) with [AuCl(PPh3)] leads to the preparation of the d0-d8-d10early-late compounds [Cptt2Zr(-S)2{Ir(CO)2}{Au(PPh3)}] (9) and [Cptt2Zr(-S)2{Rh(CO)2}{Au(PPh3)}](10) with an open M3(3-S)(2-S) heterotrimetallic metal-sulfur framework. On the other hand, treatmentof the bis(hydrosulfido)zirconium compound [Cptt2Zr(SH)2] with triethylamine followed by addition of[Pd(-Cl)(3-C3H5)]2 or [AuCl(PPh3)] affords the sulfido-bridged early-late heterobimetallic compounds[Cptt2Zr(3-S)2{Pd(3-C3H5)}2] (11) and [Cptt2Zr(-S)2{Au(PPh3)}2] (12). The molecular structure ofcomplexes 9 and 12 determined by X-ray diffraction methods are also described.