title: Comparative studies on the contribution of NHS hydrogen bonds in tungsten and molybdenum benzenedithiolate complexes.
abstract: A series of monooxotungsten(iv) and dioxotungsten(vi) benzenedithiolates, (NEt4)2[WIVO(1,2-S2-3-RCONHC6H3)2] (1-W; R = CH3(a), t-Bu (b), or CF3(c)) and (NEt4)2[WVIO2(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 NHS 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.
authors.affiliation: Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan. tokamura@chem.sci.osaka-u.ac.jp.
authors.forename: Taka-Aki
authors.identifier: http://orcid.org/0000-0002-9005-4015
authors.initials: TA
authors.lastname: Okamura
authors.affiliation: Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan. tokamura@chem.sci.osaka-u.ac.jp.
authors.forename: Yui
authors.initials: Y
authors.lastname: Omi
authors.affiliation: Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan. tokamura@chem.sci.osaka-u.ac.jp.
authors.forename: Yasunori
authors.initials: Y
authors.lastname: Hirano
authors.affiliation: Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan. tokamura@chem.sci.osaka-u.ac.jp.
authors.forename: Kiyotaka
authors.initials: K
authors.lastname: Onitsuka