Dithiolanes and Oxathiolanes Obtained from Cymantrene Derivatives: Synthesis and Properties

Abstract Novel cymantrene derivatives containing dithiolane and oxathiolane five‐membered cycles were prepared. Their spectral, optical, and redox properties were investigated by NMR, IR, UV–vis spectroscopy, and CV. Under the conditions of irradiation and subsequent dark reaction, the effect of ligand exchange on physicochemical properties was studied. Photolysis of tricarbonyl complexes leads to the formation of rare, stable four‐membered chelate complexes with Mn─S bond, one of which has been successfully isolated and characterized by X‐ray. However, in the presence of a competitive external ligand (L), the Mn─S bond dissociated, followed by the formation of new dicarbonyl complexes with the Mn─L bond, that shows the hemilabile nature of the Mn─S bond in chelate complexes.