Synthesis, electrochemistry, geometric and electronic structure of oxo-molybdenum compounds involved in an oxygen atom transferring system
Journal of Inorganic Biochemistry
Electrochemistry, Molybdenum compounds, Molybdenum enzymes, Oxygen atom transfer, Reaction intermediate, Structure
The oxygen atom transfer reactivity of Tp*MoO2(SPh) (1) (where Tp* = hydrotris-(3,5-dimethylpyrazol-1-yl)borate) with trimethyl phosphine (PMe3) has been investigated. The reaction proceed through a diamagnetic phosphoryl intermediate complex, Tp*MoO(SPh)(OPMe3) (2), which has been isolated and characterized by IR, NMR, UV-visible spectroscopy, and mass spectrometry. The molecular structure of 2 has been determined by X-ray crystallography. The complex crystallizes in monoclinic (P21/n) space group, a = 19.81 (1) Å, b = 11.1 (4) Å, c = 18.416 (5) Å, β = 121.2 (3)°, V = 3463.8 (25) Å3 with Z = 4. In acetonitrile, complex 2 exchanges its phosphoryl ligand with a solvent molecule resulting in Tp*MoO(SPh)(MeCN) (3), which has been isolated and also characterized spectroscopically and by X-ray crystallography. Compound 3 crystallizes in triclinic (P over(1, ̄)) space group, a = 10.159 (6) Å, b = 18.563 (5) Å, c = 7.986 (3) Å, α = 96.22 (3)°, β = 121.2 (3)°, γ = 84.64 (3)°, V = 1452.4 (11) Å3 with Z = 2. The electronic structures of the complexes have been investigated by density functional theory and the redox chemistry has been investigated by cyclic and differential pulse voltammetry. In acetonitrile, complex 2 spontaneously transforms to complex, 3 at a rate of 5.6 × 10-4 s-1. © 2007 Elsevier Inc. All rights reserved.
Sengar, R., Nemykin, V., & Basu, P. (2008). Synthesis, electrochemistry, geometric and electronic structure of oxo-molybdenum compounds involved in an oxygen atom transferring system. Journal of Inorganic Biochemistry, 102 (4), 748-756. https://doi.org/10.1016/j.jinorgbio.2007.11.010