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Inorg Chem. 2012 Mar 19;51(6):3436-42. doi: 10.1021/ic2020397. Epub 2012 Feb 28.

Substrate and metal control of barrier heights for oxo transfer to Mo and W bis-dithiolene sites.

Author information

1
Department of Chemistry, Stanford University, Stanford, California 94305, USA.

Abstract

Reaction coordinates for oxo transfer from the substrates Me(3)NO, Me(2)SO, and Me(3)PO to the biologically relevant Mo(IV) bis-dithiolene complex [Mo(OMe)(mdt)(2)](-) where mdt = 1,2-dimethyl-ethene-1,2-dithiolate(2-), and from Me(2)SO to the analogous W(IV) complex, have been calculated using density functional theory. In each case, the reaction first proceeds through a transition state (TS1) to an intermediate with substrate weakly bound, followed by a second transition state (TS2) around which breaking of the substrate X-O bond begins. By analyzing the energetic contributions to each barrier, it is shown that the nature of the substrate and metal determines which transition state controls the rate-determining step of the reaction.

PMID:
22372518
PMCID:
PMC3319056
DOI:
10.1021/ic2020397
[Indexed for MEDLINE]
Free PMC Article

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