Selective and Effective Stabilization of MoVI鈺怬 Bonds by NH路路路S Hydrogen Bonds via Trans Influence
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- 作者：Taka-aki Okamura ; Miki Tatsumi ; Yui Omi ; Hitoshi Yamamoto ; Kiyotaka Onitsuka
- 刊名：Inorganic Chemistry
- 出版年：2012
- 出版时间：November 5, 2012
- 年：2012
- 卷：51
- 期：21
- 页码：11688-11697
- 全文大小：449K
- 年卷期：v.51,no.21(November 5, 2012)
- ISSN：1520-510X
文摘
A monooxomolybdenum(IV) complex containing two intramolecular NH路路路S hydrogen bonds, (NEt4)2[MoIVO(1,2-S2-3-t-BuNHCOC6H3)2], was synthesized. The trans isomer was crystallized as the major product, and the molecular structure was determined by X-ray analysis. The trans isomer was isomerized by heating in solution to give a 1:1 mixture of trans and cis isomers. Oxidation of these isomers by Me3NO afforded (NEt4)2[MoVIO2(1,2-S2-3-t-BuNHCOC6H3)2]. 1H NMR analysis revealed that the dioxomolybdenum(VI) complex existed as a single isomer where both oxo ligands were trans to each of the two hydrogen-bonded thiolate ligands. The MoVI鈺怬 bond was effectively stabilized by the NH路路路S hydrogen bond via trans influence, which was determined using resonance Raman spectroscopy. These results were supported by preliminary density functional theory calculations.