Synthesis, Structural Characterization, and Theoretical Studies of Silver(I) Complexes of Dihydrobis(2‐mercapto‐benzothiazolyl) Borate

The complexes [Ag{κ 3 ‐S,S′,H‐H 2 B(mbz) 2 }(P R 3 )] x , ( 1 : x = 2, R = Ph; 2 : x = 1, R = Cy) (mbz = 2‐mercaptobenzothiazolyl) and amidine based dihydro(2‐mercaptobenzo‐thiazolyl) borates, [HN=C(Ph)–NH( R )–H 2 B(mbz)] ( 3 : R = 2,6‐diisopropylphenyl and 4 : R = Ph) were synthesized and characterized by various spectroscopic methods and single‐crystal X‐ray crystallography. Complex [Ag{κ 3 ‐S,S′,H‐H 2 B(mbz) 2 }(PPh 3 )] 2 ( 1 ) has a dimeric structure in its crystalline state, in which central silver(I) atoms adopt a distorted trigonal bipyramid arrangement. In contrast, complex [Ag{κ 3 ‐S,S′,H‐H 2 B(mbz) 2 }(PCy 3 )] ( 2 ) has a monomeric structure in its crystalline state, in which the central silver(I) atoms adopt a distorted trigonal planar arrangement. Infrared spectroscopy was utilized as a tool for investigating the presence of M ··· H–B interactions. In addition, density functional theory (DFT) calculations were used to analyse the B–H ··· [ M ] bonding interaction in the metal borate complexes.