The thermolysis of [(C 5 H 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 5 H 4 )SiMe 2 (N-t-Bu)]Ti[(o-C 6 H 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 5 H 4 )SiMe 2 (N-t-Bu)]Ti[(o-C 6 H 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.