449778-49-8Relevant articles and documents
Electrophilic addition of Ph3PAu+ to anionic alkoxy Fischer-type carbene complexes: A novel approach to metal-stabilized bimetallic vinyl ether complexes
Raubenheimer, Helgard G.,Esterhuysen, Matthias W.,Timoshkin, Alexey,Chen, Yu,Frenking, Gernot
, p. 3173 - 3181 (2002)
The addition of the Ph3PAu+ electrophile to deprotonated Fischer-type alkoxy(methyl)-carbene complexes of pentacarbonyl group 6 metals leads to the formation of novel vinyl ether complexes of gold coordinated to the pentacarbonylmetal moiety. X-ray structures and DFT calculations show that the greatest bonding contribution in the vinyl coordination to the M(CO)5 fragment comes from the terminal, partially negatively charged, CH2 carbon atom via partial end-on η1-bonding rather than the usual η2-bonding of olefins. The corresponding positive charge from the asymmetric vinyl coordination is mainly delocalized onto the Ph3PAu fragment, stabilizing this coordination mode. The use of W instead of Cr in the M(CO)5 fragment, in otherwise isostructural compounds, results in somewhat greater asymmetry in the vinyl coordination, with the difference in the two M(CO)5-η2-vinyl carbon bond lengths increasing from 0.252(11) A? (M = Cr) to 0.307(5) A? (M = W) in the solid state.
