Selective and Effective Stabilization of MoVI═O Bonds by NH···S Hydrogen Bonds via Trans Influence
| Autor: | Hitoshi Yamamoto, Kiyotaka Onitsuka, Miki Tatsumi, Taka-aki Okamura, Yui Omi |
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| Rok vydání: | 2012 |
| Předmět: |
Models
Molecular Molybdenum Magnetic Resonance Spectroscopy Sulfur Compounds Chemistry Stereochemistry Trans effect Hydrogen bond Resonance Raman spectroscopy Hydrogen Bonding Crystallography X-Ray Spectrum Analysis Raman Medicinal chemistry Oxygen Inorganic Chemistry Isomerism Coordination Complexes Intramolecular force Proton NMR Molecule Density functional theory Physical and Theoretical Chemistry Oxidation-Reduction Cis–trans isomerism Hydrogen |
| Zdroj: | Inorganic Chemistry. 51:11688-11697 |
| ISSN: | 1520-510X 0020-1669 |
| DOI: | 10.1021/ic301597d |
| Popis: | A monooxomolybdenum(IV) complex containing two intramolecular NH···S hydrogen bonds, (NEt(4))(2)[Mo(IV)O(1,2-S(2)-3-t-BuNHCOC(6)H(3))(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 Me(3)NO afforded (NEt(4))(2)[Mo(VI)O(2)(1,2-S(2)-3-t-BuNHCOC(6)H(3))(2)]. (1)H 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 Mo(VI)═O bond was effectively stabilized by the NH···S hydrogen bond via trans influence, which was determined using resonance Raman spectroscopy. These results were supported by preliminary density functional theory calculations. |
| Databáze: | OpenAIRE |
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