om9610410_si_001.pdf (1.42 MB)
Competitive Acetylide C−C Bond Scission vs Formation of a Quadruply Bridging Carbonyl Ligand. X-ray Crystal Structures of the Two Pentanuclear Clusters Cp*3W3Ru2(μ4-C)(μ3-CPh)(CO)9 and Cp*3W3Ru2(μ3-CCBut)(CO)9
journal contribution
posted on 1997-04-29, 00:00 authored by Pei-Chiun Su, Yun Chi, Chi-Jung Su, Shie-Ming Peng, Gene-Hsiang LeeReactions of Cp*WRu2(CCPh)(CO)8
(1a) with excess Cp*W(CO)3H, Cp* =
C5Me5, affords
a carbido−alkylidyne cluster
Cp*3W3Ru2(μ4-C)(μ3-CPh)(CO)9
(5) alone with three byproducts,
which are identified as hydride cluster
Cp*WRu3(μ-H)3(CO)11
(2), vinylidene cluster
Cp*2W2Ru2(CCHPh)(CO)9 (4), and a
pentanuclear oxo−carbido cluster
Cp*2W2(O)Ru3(μ5-C)(CO)11
(3). In contrast, the respective condensation using
tert-butyl derivative Cp*WRu2(CCBut)(CO)8 (1b) gives an acetylide
cluster
Cp*3W3Ru2(μ3-CCBut)(CO)9
(6). The X-ray
structural determinations of 5 and 6 reveals the
existence of an edge-bridged tetrahedral
core, in which the butterfly crater is occupied by a
μ4-carbide in 5 or a quadruply
bridging
CO ligand in 6. A plausible mechanism leading to the
formation of these two cluster
compounds is also presented.