Sunlight Photolysis of Decamethyltitanocene Dihydrosulfide Affords the Titanium Sulfide Cage Clusters (Cp~*Ti)_6S_8 and (Cp~*Ti)_4S_6

摘要

Sunlight photolysis of decamethyltitanocene dihydrosulfide [Cp~*_2Ti(SH)_2] (1, Cp~* = η_5-C_5Me_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~*_2Ti(OH)_2] by U. Rosenthal et al.