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

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 S2Cl2 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.