Title

Crystal structures of MoCl < inf> 2 (O)(O < inf> 2 )(OPMePh < inf> 2 ) < inf> 2 and mixtures of MoCl < inf> 2 (O < inf> 2 ) (OPPh < inf> 3 ) < inf> 2 and MoCl < inf> 2 (O)(O < inf> 2 )(OPPh < inf> 3 ) < inf> 2 : Allylic alcohol isomerization studies using MoCl < inf> 2 (O)(O < inf> 2 )(OPMePh < inf> 2 ) < inf> 2

Document Type

Article

Publication Date

3-1-2005

Abstract

Adding one equivalent of H2O2 to compounds of stoichiometry MoCl2(O)2(OPR3)2, OPR3 = OPMePh2 or OPPh3, leads to the formation of oxo-peroxo compounds MoCl2(O)(O2)(OPR 3)2. The compound MoCl2(O)(O 2)(OPMePh2)2 crystallized with an unequal disorder, 63%:37%, between the oxo and peroxo ligands, as verified by single-crystal X-ray diffractometry, and can be isolated in reasonable yields. MoCl2(O)(O2)(OPPh3)2, was not isolated in pure form, co-crystallized with MoCl2(O) 2(OPPh3)2 in two ratios, 18%:82% and 12%:88%, respectively, and did not contain any disorder in the arrangement of the oxo and peroxo groups. These complexes accomplish the isomerization of various allylic alcohols. A mechanism of this reaction has been constructed based on 18O isotopic studies and involves exchange between the alcohol and metal bonded O atoms. © 2004 Elsevier B.V. All rights reserved.

Publication Title

Inorganica Chimica Acta

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