Comparative studies on the contribution of NH⋯S hydrogen bonds in tungsten and molybdenum benzenedithiolate complexes

Abstract

A series of monooxotungsten(IV) and dioxotungsten(VI) benzenedithiolates, (NEt₄)₂[W^IVO(1,2-S₂-3-RCONHC₆H₃)₂] (1-W; R = CH₃ (a), t-Bu (b), or CF₃ (c)) and (NEt₄)₂[W^VIO₂(1,2-S₂-3-RCONHC₆H₃)₂] (2-W), were synthesized and compared with the corresponding molybdenum analogues. Single crystals of trans-1b-W were successfully obtained, and the crystal structure was determined by X-ray analysis although 1b-Mo could not be crystallized. The NH⋯S hydrogen bonds shifted the potential of the W(IV/V) redox couple to more positive values, and the strength of the hydrogen bond and the positive shift value were strongly correlated. The hydrogen bonds in both 1-W and 2-W were weaker than those in the corresponding molybdenum analogues; however, the effect of the hydrogen bonds on the redox potential was greater in 1-W.