Sunlight Photolysis of Decamethyltitanocene Dihydrosulfide Affords the Titanium Sulfide Cage Clusters (Cp*Ti) 6 S 8 and (Cp*Ti) 4 S 6

Sunlight photolysis of decamethyltitanocene dihydrosulfide [Cp* 2 Ti(SH) 2 ] ( 1 , Cp* = η 5 ‐C 5 Me 5 ) in toluene affords the titanium sulfide clusters [(Cp*Ti) 6 (μ 3 ‐S) 8 ] ( 4 ) and [(Cp*Ti) 4 (μ 3 ‐S) 3 (μ 2 ‐S) 3 ] ( 5 ), the former in very low yield and the latter in good yield. The crystal structures of both compounds are toluene solvates and are based on a nearly regular titanium octahedron for 4 and a trigonal pyramid for 5 . The [(Cp*Ti) 3 (μ 3 ‐S)(μ 2 ‐S) 3 ] ( 6 ) complex isolated in a trace amount from the photolysis of 1 in hexane could be a precursor of 4 . A plausible mechanism for the formation of 5 and 6 follows a mechanism recently proposed for photolysis of [Cp* 2 Ti(OH) 2 ] by U. Rosenthal et al.