The addition of the Ph 3 PAu + 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, CH 2 carbon atom via partial end-on η 1 -bonding rather than the usual η 2 -bonding of olefins. The corresponding positive charge from the asymmetric vinyl coordination is mainly delocalized onto the Ph 3 PAu 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 −η 2 -vinyl carbon bond lengths increasing from 0.252(11) Å (M = Cr) to 0.307(5) Å (M = W) in the solid state.
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Raubenheimer et al. (2002) studied this question.