Abstract
Agostic bonds have proliferated since the first insightful review by Brookhart and Green in 1983. Numerous {alpha}-agostic carbenes, alternatively described as protonated carbynes, of both groups V{sup 3} and VI{sup 4} have been reported by Schrock and co-workers. The paradigm for olefin insertion and polymerization reactions involves {beta}-agostic alkyls. Four-electron-donor alkyne ligands, common for group VI, provide access to {eta}{sup 2}-vinyl ligands which are precursors to {beta}-agostic carbene products as reported here. Addition of a nucleophile (H{sup {minus}}, Me{sup {minus}}) to the terminal carbon of the phenylacetylene ligand in (Tp{prime}(CO){sub 2}W(PhC{triple bond}CH))(BF{sub 4})(Tp{prime} = hydridotris(3,5-dimethylpyrazolyl)borate) forms an {eta}{sup 2}-vinyl ligand which can be protonated to form an alkylphenylcarbene ligand. The agostic bond present in (Tp{prime}(CO){sub 2}W{double bond}C(Ph)CH{sub 2}R)(BF{sub 4}) (R = H, Me), described in detail below, complements the range of saturated and unsaturated agostic ligands represented.
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