Ten-Electron Coordination and Reactivity of an Arylphosphinidene Ligand
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- 作者：M. Esther Garcí ; a ; Ví ; ctor Riera ; Miguel A. Ruiz ; David Sá ; ez ; Hayrullo Hamidov ; John C. Jeffery ; and Thomas Riis-Johannessen
- 刊名：Journal of the American Chemical Society
- 出版年：2003
- 出版时间：October 29, 2003
- 年：2003
- 卷：125
- 期：43
- 页码：13044 - 13045
- 全文大小：72K
- 年卷期：v.125,no.43(October 29, 2003)
- ISSN：1520-5126
文摘
Photochemical decarbonylation of [Mo2Cp2(
-PR*)(CO)4] (Cp = 
5-C5H5; R* = 2,4,6-C6H2tBu3) gives [Mo2Cp2(-
1:1,6-PR*)(CO)2], which shows the first example of a remarkable 10-electron donor arylphosphinidene ligand which bridges two Mo atoms through its phosphorus atom while being 
-bonded to one Mo center through the six carbon atoms of the aryl ring. This causes a severe pyramidal distortion of the P-bound C atom. The complex adds CO to give [Mo2Cp2(-1:1,4-PR*)(CO)3], which has an 8-electron donor PR* ligand, and then the parent complex [Mo2Cp2(-PR*)(CO)4]. Protonation of [Mo2Cp2(-1:1,6-PR*)(CO)2] gives the hydride [Mo2Cp2(H)(-1:1,6-PR*)(CO)2]+, which undergoes P-C bond cleavage and hydride migration, affording the phosphido cation [Mo2Cp2(-P)(6-R*H)(CO)2]+.
-PR*)(CO)4] (Cp = 5-C5H5; R* = 2,4,6-C6H2tBu3) gives [Mo2Cp2(-1:1,6-PR*)(CO)2], which shows the first example of a remarkable 10-electron donor arylphosphinidene ligand which bridges two Mo atoms through its phosphorus atom while being -bonded to one Mo center through the six carbon atoms of the aryl ring. This causes a severe pyramidal distortion of the P-bound C atom. The complex adds CO to give [Mo2Cp2(-1:1,4-PR*)(CO)3], which has an 8-electron donor PR* ligand, and then the parent complex [Mo2Cp2(-PR*)(CO)4]. Protonation of [Mo2Cp2(-1:1,6-PR*)(CO)2] gives the hydride [Mo2Cp2(H)(-1:1,6-PR*)(CO)2]+, which undergoes P-C bond cleavage and hydride migration, affording the phosphido cation [Mo2Cp2(-P)(6-R*H)(CO)2]+.