Abstract
The thermolysis of [(C 5H 4)SiMe 2(N- t-Bu)]TiPh 2 in the presence of diphenylacetylene proceeds at 80 °C in cyclohexane solution with the sole formation of the titanacyclic complex [(C 5H 4)SiMe 2(N- t-Bu)]Ti[( o-C 6H 4)C(Ph) C(Ph)], which has been characterized by solution NMR measurements and X-ray crystallographic analysis. This reaction is accompanied by the elimination of benzene and presumably occurs via coupling of a titanium benzyne intermediate with diphenylacetylene. The two chemically inequivalent Ti–C bonds of 2.081(7) and 2.103(6) Å in [(C 5H 4)SiMe 2(N- t-Bu)]Ti[( o-C 6H 4)C(Ph) C(Ph)] reflect the increased electrophilicity of the d 0 Ti(IV) center arising from the presence of the bifunctional ansa-cyclopentadienyldimethylsilylamido ligand.
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