Reversible Opening of the Triangular Structure of a Sulfido-Bridged ZrRh2 Early-Late Heterobimetallic Complex Induced by Bis-(diphenylphosphino)methane
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- 作者：Marc A. F. Hernandez-Gruel ; Fernando J. Lahoz ; Isabel T. Dobrinovich ; F. Javier Modrego ; Luis A. Oro ; Jesú ; s J. Pé ; rez-Torrente
- 刊名：Organometallics
- 出版年：2007
- 出版时间：May 7, 2007
- 年：2007
- 卷：26
- 期：10
- 页码：2616 - 2622
- 全文大小：180K
- 年卷期：v.26,no.10(May 7, 2007)
- ISSN：1520-6041
文摘
Reaction of the early-late heterobimetallic complexes [Cptt2Zr(
images/entities/mgr.gif">3-S)2{M(CO)}2(images/entities/mgr.gif">-dppm)] (M = Rh,Ir) with dppm (bis-(diphenylphosphino)methane) yields the compounds [Cptt2Zr(images/entities/mgr.gif">-S)2M(images/entities/mgr.gif">-CO)2(images/entities/mgr.gif">-dppm)M(images/gifchars/eta.gif" BORDER=0 >2-dppm)] (M = Rh (3), Ir (4)). The molecular structure of 3 shows a bent trimetallic ZrRhRhchain with tetrahedral, trigonal-bipyramidal, and square-pyramidal geometries, respectively. This trinuclearcompound exhibits a mixed-valence Rh(II)-Rh(0) metal-metal bonded unit that results from the unusualchelating coordination of the metalloligand [Cptt2Zr(S)2]2- and is further stabilized by the presence oftwo unsymmetrical bridging carbonyl ligands, which interact with the unsaturated Rh(II) metal. Theformation of 3 is reversible, and the equilibrium 1 + dppm images/entities/lrarr2.gif"> 3 has been observed in solution (K images/entities/ap.gif"> 16at 22 images/entities/deg.gif">C in C6D6). The opening of the triangular core in the heterotrimetallic compound [Cptt2Zr(images/entities/mgr.gif">3-S)2{Rh(CO)}{Ir(CO)}(images/entities/mgr.gif">-dppm)] (5) is not selective and gives the compounds [Cptt2Zr(images/entities/mgr.gif">-S)2Rh(images/entities/mgr.gif">-CO)2(images/entities/mgr.gif">-dppm)Ir(images/gifchars/eta.gif" BORDER=0 >2-dppm)] (6) and [Cptt2Zr(images/entities/mgr.gif">-S)2Ir(images/entities/mgr.gif">-CO)2(images/entities/mgr.gif">-dppm)Rh(images/gifchars/eta.gif" BORDER=0 >2-dppm)] (7) in a 3:1 molar ratio.