Selective and effective stabilization of Mo(VI)═O bonds by NH···S hydrogen bonds via trans influence.
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.
Department of Macromolecular Science, Graduate School of Science, Osaka University, Toyonaka, Osaka 560-0043, Japan. tokamura@chem.sci.osaka-u.ac.jp
Taka-aki
TA
Okamura
Miki
M
Tatsumi
Yui
Y
Omi
Hitoshi
H
Yamamoto
Kiyotaka
K
Onitsuka
D056831:Coordination Complexes / Q000138:chemical synthesis / Q000737:chemistry*; D018360:Crystallography, X-Ray; D006859:Hydrogen / Q000737:chemistry*; D006860:Hydrogen Bonding; D007536:Isomerism; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D008982:Molybdenum / Q000737:chemistry*; D010084:Oxidation-Reduction; D010100:Oxygen / Q000737:chemistry*; D013059:Spectrum Analysis, Raman; D013457:Sulfur Compounds / Q000138:chemical synthesis / Q000737:chemistry*
D056831:Coordination Complexes; D013457:Sulfur Compounds; D006859:Hydrogen; D008982:Molybdenum; D010100:Oxygen