Ligand-coupling assembly of Re(i)-thiolate complexes

Abstract

By taking advantage of solvothermal reactions of Re₂(CO)₁₀ with 2-mercaptobenzothiazol (HNS₂) or 2-mercaptobenzoxazol (HNOS), a series of Re(I) complexes (1–4) with in situ ligands were synthesized and structurally characterized by X-ray diffraction. In this study, we examined the effects of reaction conditions (i.e., reaction solvents and temperatures) on the HNS₂ system to give complexes 1–3, and also compared the reaction products of the HNS₂ (2) and HNOS (4) systems under similar reaction conditions. For the HNS₂ system, the reaction temperatures at 140 and 120 °C in mesitylene led to different ligands in complexes 1 and 2, respectively. However, at the same temperature of 140 °C, different solvents (mesitylene or benzene) caused the formation of complexes 1 and 3 containing different ligands, respectively. Although the same temperature and solvent were used, HNS₂ and HNOS underwent a similar in situ ligand reaction in dinuclear complexes 2 and 4, which surprisingly show both anti and syn conformations, respectively.