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https://hdl.handle.net/2440/66166
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Type: | Journal article |
Title: | Oxygen Atom Transfer in Models for Molybdenum Enzymes: Isolation and Structural, Spectroscopic, and Computational Studies of Intermediates in Oxygen Atom Transfer from Molybdenum(VI) to Phosphorus(III) |
Author: | Millar, A. Doonan, C. Smith, P. Nemykin, V. Basu, P. Young, C. |
Citation: | Chemistry: A European Journal, 2005; 11(11):3255-3267 |
Publisher: | Wiley-V C H Verlag GMBH |
Issue Date: | 2005 |
ISSN: | 0947-6539 1521-3765 |
Statement of Responsibility: | Andrew J. Millar, Christian J. Doonan, Paul D. Smith, Victor N. Nemykin, Partha Basu, and Charles G. Young |
Abstract: | Intermediates in the oxygen atom transfer from Mo(VI) to P(III), [Tp(iPr)MoOX(OPR3)] (Tp(iPr) = hydrotris(3-isopropylpyrazol-1-yl)borate; X = Cl-, phenolates, thiolates), have been isolated from the reactions of [Tp(iPr)MoO2X] with phosphines (PEt3, PMePh2, PPh3). The green, diamagnetic oxomolybdenum(IV) complexes possess local C(1) symmetry (by NMR spectroscopy) and exhibit IR bands assigned to nu(Mo==O) (approximately 950 cm(-1)) and nu(P==O) (1140-1083 cm(-1)) vibrations. The X-ray crystal structures of [Tp(iPr)MoOX(OPEt3)] (X = OC6H4-2-sBu, SnBu), [Tp(iPr)MoO(OPh)(OPMePh2)], and [Tp(iPr)MoOCl(OPPh3)] have been determined. The monomeric complexes exhibit distorted octahedral geometries, with coordination spheres composed of tridentate fac-Tp(iPr) and mutually cis monodentate terminal oxo, phosphoryl (phosphine oxide), and monoanionic X ligands. The electronic structures and stabilities of the complexes have been probed by computational methods, with the three-dimensional energy surfaces confirming the existence of a low-energy steric pocket that restricts the conformational freedom of the phosphoryl ligand and inhibits complete oxygen atom transfer. The reactivity of the complexes is also briefly described. |
Keywords: | bioinorganic chemistry electronic structure molybdenum oxygen atom transfer phosphoryl ligands |
Rights: | Copyright © 2005 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim |
DOI: | 10.1002/chem.200401101 |
Published version: | http://dx.doi.org/10.1002/chem.200401101 |
Appears in Collections: | Aurora harvest Chemistry publications Environment Institute publications |
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