학술논문
Structural Studies of Mono- and Dimetallic MoVI Complexes − A New Mechanistic Contribution in Catalytic Olefin Epoxidation Provided by Oxazoline Ligands
Document Type
Article
Author
Source
European Journal of Inorganic Chemistry; November 2004, Vol. 2004 Issue: 21 p4278-4285, 8p
Subject
Language
ISSN
14341948; 10990682
Abstract
New seven-coordinate oxo(peroxo)molybdenum(VI) complexes with bidentate chiral oxazolines, anionic κ2-N,O (V) and neutral κ2-N,N (VI), have been prepared and fully characterised by NMR spectroscopy and single-crystal X-ray diffraction studies. Dimetallic dioxo(μ-oxo)molybdenum(VI) compounds containing oxazolinylpyridine ligands II−IV have also been synthesised. NMR studies showed the presence of several isomers (up to six species) due to the Mo−O−Mo bridge angle and the unsymmetrical nature of the N,N ligand. The roles of mono- (I, V and VI) and dimetallic (II) oxomolybdenum(VI) complexes in the catalytic epoxidation of cyclooctene, norbornene and (R)-limonene have been studied. The high activity of the oxomono(peroxo) precursor V containing the hemilabile oxazolinylphenolate, in contrast to the unexpected low activity for the oxobis(peroxo) species VI, could be justified by the inertness observed for the oxazolinylpyridine ligand. In addition, the dimetallic system II afforded high selectivity towards limonene epoxide formation (trans/cis-10 ratio up to 9:1). (© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, Germany, 2004)