O-atom-transfer oxidation of [molybdenum(IV) oxo{3,6-(acylamino)2- 1,2-benzenedithiolato}2]2- promoted by intramolecular NH...S hydrogen bonds

Inorg Chem. 2006 Jan 23;45(2):894-901. doi: 10.1021/ic051493h.

Abstract

Novel molybdenum dithiolene compounds having neighboring amide groups as models for molybdoenzymes, (NEt(4))(2)[Mo(IV)O{1,2-S(2)-3,6-(RCONH)(2)C(6)H(2)}(2)] (R = CH(3), CF(3), t-Bu, Ph(3)C), were designed and synthesized. The contributions of the NH...S hydrogen bond to the electrochemical properties of the metal ion and the reactivity of the O-atom-transfer reaction were investigated by a comparison with [Mo(IV)O(1,2-S(2)C(6)H(4))(2)](2)(-). The MoOS(4) core of [Mo(IV)O{1,2-S(2)-3,6-(CH(3)CONH)(2)C(6)H(2)}(2)](2)(-) shows no significant geometrical difference from that of [Mo(IV)O(1,2-S(2)C(6)H(4))(2)](2)(-) in the crystal. The hydrogen bonds positively shifted the Mo(IV/V) redox potential and accelerated the reduction of Me(3)NO.

Publication types

  • Research Support, Non-U.S. Gov't

MeSH terms

  • Crystallography, X-Ray
  • Electrochemistry
  • Hydrogen Bonding
  • Methylamines / chemistry
  • Models, Molecular
  • Molecular Structure
  • Molybdenum / chemistry*
  • Organometallic Compounds / chemical synthesis*
  • Organometallic Compounds / chemistry*
  • Oxidation-Reduction
  • Oxygen / chemistry*
  • Sensitivity and Specificity
  • Spectrophotometry, Infrared / methods
  • Spectrum Analysis, Raman / methods
  • Sulfhydryl Compounds / chemistry*

Substances

  • Methylamines
  • Organometallic Compounds
  • Sulfhydryl Compounds
  • Molybdenum
  • trimethyloxamine
  • Oxygen