Ten-electron coordination and reactivity of an arylphosphinidene ligand

被引：32
作者：
García, ME
Riera, V
Ruiz, MA [1 ]
Sáez, D
Hamidov, H
Jeffery, JC
Riis-Johannessen, T
机构：
[1] Univ Oviedo, IUQOEM, Dept Quim Organ & Inorgan, E-33071 Oviedo, Spain
[2] Univ Bristol, Sch Chem, Bristol BS8 1TS, Avon, England
来源：
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2003年 / 125卷 / 43期
关键词：
D O I：
10.1021/ja037293r
中图分类号：
O6 [化学];
学科分类号：
0703 ;
摘要：
Photochemical decarbonylation of [Mo2Cp2(μ-PR*)(CO)4] (Cp = η5-C5H5; R* = 2,4,6-C6H2tBu3) gives [Mo2Cp2(μ-κ1:κ1,η6-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 π-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(μ-κ1:κ1,η4-PR*)(CO)3], which has an 8-electron donor PR* ligand, and then the parent complex [Mo2Cp2(μ-PR*)(CO)4]. Protonation of [Mo2Cp2(μ-κ1:κ1,η6-PR*)(CO)2] gives the hydride [Mo2Cp2(H)(μ-κ1:κ1,η6-PR*)(CO)2]+, which undergoes P?C bond cleavage and hydride migration, affording the phosphido cation [Mo2Cp2(μ-P)(η6-R*H)(CO)2]+. Copyright © 2003 American Chemical Society.
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页码：13044 / 13045
页数：2
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