Abstract: | The complexes [Ag{κ3‐S,S′,H‐H2B(mbz)2}(PR3)]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)–H2B(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{κ3‐S,S′,H‐H2B(mbz)2}(PPh3)]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{κ3‐S,S′,H‐H2B(mbz)2}(PCy3)] ( 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. |