Synthesis, electrochemical behavior and EPR study of organometallic [5]trovacenylthiol (η7-C7H7)V(η5-C5H4SH) and structural characterization of ansa-trithio[3]trovacenophane

Abstract Organometallic paramagnetic [5]trovacenylthiol ( 3 ) was prepared by acidification of lithium [5]trovacenylthiolate 2 , which was synthesized via elemental sulfur oxidative insertion to C–Li bond of [5]trovacenyllithium. [5]Trovacenylthiol ( 3 ) was investigated by means of cyclic voltammetry and electron paramagnetic resonance (EPR). However, the reaction of concentrated DME solution of 2 with S 2 Cl 2 unprecedentedly afforded ansa-trithio[3]trovacenophane ( 6 ), which was demonstrated by X-ray diffraction analysis. Furthermore, three efficient strategies have been explored to construct S–C, S–Si bond of organometallic alkyl, aryl [5]trovacenyl sulfides ( 7 , 8 , 9 ) and silylthioester ( 10 ) in the absence of transition-metal catalyst under mild reaction conditions.