Crystal structures of MoCl2(O)(O2)(OPMePh2)2 and mixtures of MoCl2(O2)(OPPh3)2 and MoCl2(O)(O2)(OPPh3)2: allylic alcohol isomerization studies using MoCl2(O)(O2)(OPMePh2)2 |
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| Authors: | Ge Wang |
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| Affiliation: | Department of Chemistry, Michigan Technological University, 1400 Townsend Drive, Houghton, MI 49931, USA |
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| 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)(OPR3)2. The compound MoCl2(O)(O2)(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. |
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| Keywords: | Allylic alcohol Isomerization Molybdenum oxide Peroxide Catalysts |
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