Comparative studies on the contribution of NH···S hydrogen bonds in tungsten and molybdenum benzenedithiolate complexes
Comparative studies on the contribution of NH···S hydrogen bonds in tungsten and molybdenum benzenedithiolate complexes
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NH贡献的比较研究
DOI：
10.1039/c6dt02250b
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发表时间：
2016
期刊：
影响因子：
--
通讯作者：
and K. Onitsuka
中科院分区：
文献类型：
--
作者：
T. Okamura;Y. Omi;Y. Hirano;and K. Onitsuka
合成了一系列苯二硫醇单氧钨（IV）和二氧钨（VI）配合物（NEt 4）2[WIVO（1，2-S2-3-RCONHC 6 H3）2]（1-W; R = CH 3（a），t-Bu（B），或CF 3（c））和（NEt 4）2[WVIO 2（1，2-S2-3-RCONHC 6 H3）2]（2-W），并与相应的钼类似物进行了比较。成功地获得了反式-1b-W的单晶体，虽然1b-Mo不能结晶，但通过X射线分析确定了晶体结构。NH → S氢键使W（IV/V）氧化还原电对的电位向更正的值移动，且氢键强度与正移值有很强的相关性。1-W和2-W中的氢键比相应的钼类似物中的氢键弱;然而，氢键对氧化还原电位的影响在1-W中更大。
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 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.