Sunlight Photolysis of Decamethyltitanocene Dihydrosulfide Affords the Titanium Sulfide Cage Clusters (Cp*Ti)6S8 and (Cp*Ti)4S6
2013
Abstract
Sunlight photolysis of decamethyltitanocene dihydrosulfide [Cp*2Ti(SH)2] (1, Cp* = 5-C5Me5) in toluene affords the titanium sulfide clusters [(Cp*Ti)6(3-S)8] (4) and [(Cp*Ti)4(3-S)3(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(3-S)(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.