A Density Functional Study of Oxygen Atom Transfer Reactions between Biological Oxygen Atom Donors and Molybdenum(IV) Bis(dithiolene) Complexes

Citations Over TimeTop 10% of 2002 papers

Abstract

Density functional calculations have been used to investigate oxygen atom transfer reactions from the biological oxygen atom donors trimethylamine N-oxide (Me(3)NO) and dimethyl sulfoxide (DMSO) to the molybdenum(IV) complexes [MoO(mnt)(2)](2-) and [Mo(OCH(3))(mnt)(2)](-) (mnt = maleonitrile-1,2-dithiolate), which may serve as models for mononuclear molybdenum enzymes of the DMSO reductase family. The reaction between [MoO(mnt)(2)](2-) and trimethylamine N-oxide was found to have an activation energy of 72 kJ/mol and proceed via a transition state (TS) with distorted octahedral geometry, where the Me(3)NO is bound through the oxygen to the molybdenum atom and the N-O bond is considerably weakened. The computational modeling of the reactions between dimethyl sulfoxide (DMSO) and [MoO(mnt)(2)](2-) or [Mo(OCH(3))(mnt)(2)](-) indicated that the former is energetically unfavorable while the latter was found to be favorable. The addition of a methyl group to [MoO(mnt)(2)](2-) to form the corresponding des-oxo complex not only lowers the relative energy of the products but also lowers the activation energy. In addition, the reaction with [Mo(OCH(3))(mnt)(2)](-) proceeds via a TS with trigonal prismatic geometry instead of the distorted octahedral TS geometry modeled for the reaction between [MoO(mnt)(2)](2-) and Me(3)NO.

Related Papers

• → Amines in Fish Muscle: II. Development of Trimethylamine and Other Amines(1945)137 cited
• → Structural and electronic data of three first-row transition octahedral hexaaquametal(II) ions, metal=Cr, Ni or Cu(2018)9 cited
• → A Pilot Study of the Effect of (E, E)-2, 4-Undecadienal on the Offensive Odour of Trimethylamine(2012)4 cited
• → Trimethylamine‐Haloboranes(1970)12 cited
• → The Crystal Structure of Ludlamite(1949)