TY - DATA T1 - A Density Functional Study of Oxygen Atom Transfer Reactions between Biological Oxygen Atom Donors and Molybdenum(IV) Bis(dithiolene) Complexes PY - 2002/11/16 AU - Anders Thapper AU - Robert J. Deeth AU - Ebbe Nordlander UR - https://acs.figshare.com/articles/journal_contribution/A_Density_Functional_Study_of_Oxygen_Atom_Transfer_Reactions_between_Biological_Oxygen_Atom_Donors_and_Molybdenum_IV_Bis_dithiolene_Complexes/3606261 DO - 10.1021/ic020385h.s001 L4 - https://ndownloader.figshare.com/files/5694306 KW - mnt KW - MoO KW - Density Functional Study KW - octahedral TS geometry KW - molybdenum KW - oxygen atom transfer reactions KW - Mo KW - DMSO reductase family KW - Oxygen Atom Transfer Reactions KW - Biological Oxygen Atom Donors KW - dimethyl sulfoxide KW - oxygen atom donors trimethylamine N KW - activation energy N2 - Density functional calculations have been used to investigate oxygen atom transfer reactions from the biological oxygen atom donors trimethylamine N-oxide (Me3NO) and dimethyl sulfoxide (DMSO) to the molybdenum(IV) complexes [MoO(mnt)2]2- and [Mo(OCH3)(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 Me3NO 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(OCH3)(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(OCH3)(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 Me3NO. ER -