Issue 6, 2004
From the journal:

Dalton Transactions

Mixed crystals containing the dioxo complex [{Ph3SiO}2VO2]− and novel pentacoordinated oxoperoxo complex [{Ph3SiO}2VO(O2)]−: X-ray crystal structure and assessment as oxidation catalysts

Maxence Vennat,*a   Jean-Marie Brégeault*a  and  Patrick Hersonb  

* Corresponding authors

a Laboratoire des Systèmes Interfaciaux à l'Echelle Nanométrique, Université Pierre et Marie Curie/CNRS, case 196, 4 place Jussieu, 75252 Paris cedex 05, France
E-mail: bregeaul@ccr.jussieu.fr, maxencevennat@yahoo.fr
Fax: +33 (0) 1 44 27 55 36

b Chimie Inorganique et Matériaux Moléculaires, Université Pierre et Marie Curie/CNRS, case 42, 4 place Jussieu, 75252 Paris cedex 05, France
E-mail: herson@ccr.jussieu.fr

Abstract

[n-Bu4N][{Ph3SiO}2VO2] reacts with H2O2 to yield an oxoperoxo complex which crystallizes as a mixed-crystal compound, [P(C6H5)4][{(C6H5)3 SiO}2VO2]x[{(C6H5)3 SiO}2VO(O2)]1−x, 1 (x = 0.57). It has been characterized by elemental analysis and spectroscopy (51V NMR, UV-visible and IR). The X-ray structure analysis reveals the presence of two interrelated anions: [{Ph3SiO}2VVO2]−, 1a, and [{Ph3SiO}2VVO(O2)]−, 1b with a cisoid geometry of the {VO(O2)}+ moiety. The two structures differ only slightly: anion 1a exhibits unusual tetrahedral coordination around the vanadium centre found in the precursor, whereas the geometry at the metal ion in 1b can be described as a trapezoidal pyramid. Steric constraints due to Ph3SiO− ligands and PPh4+ cations are responsible for this geometry. The reactivity of 1 in the C–C bond cleavage of 2-methylcyclohexanone under anaerobic conditions has been studied. The results suggest that peroxygen species are involved in the oxidative cleavage of C–C bonds of cycloalkanones.

Graphical abstract: Mixed crystals containing the dioxo complex [{Ph3SiO}2VO2]− and novel pentacoordinated oxoperoxo complex [{Ph3SiO}2VO(O2)]−: X-ray crystal structure and assessment as oxidation catalysts

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Article information

DOI
https://doi.org/10.1039/B400657G
Article type
Paper
Submitted
14 Jan 2004
Accepted
04 Feb 2004
First published
16 Feb 2004

Dalton Trans., 2004, 908-913

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Mixed crystals containing the dioxo complex [{Ph3SiO}2VO2]− and novel pentacoordinated oxoperoxo complex [{Ph3SiO}2VO(O2)]−: X-ray crystal structure and assessment as oxidation catalysts

M. Vennat, J. Brégeault and P. Herson, Dalton Trans., 2004, 908 DOI: 10.1039/B400657G

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