1. Synthesis and Evaluation of Molybdenum and Tungsten Monoaryloxide Halide Alkylidene Complexes for Z-Selective Cross-Metathesis of Cyclooctene and Z-1,2-Dichloroethylene
- Author
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Jonathan K. Lam, Congqing Zhu, Richard R. Schrock, Konstantin V. Bukhryakov, Amir H. Hoveyda, and Peter Müller
- Subjects
Models, Molecular ,Nitrile ,chemistry.chemical_element ,010402 general chemistry ,Metathesis ,01 natural sciences ,Biochemistry ,Medicinal chemistry ,Catalysis ,Tungsten ,chemistry.chemical_compound ,Cyclooctanes ,Colloid and Surface Chemistry ,Halogens ,Cyclooctene ,Coordination Complexes ,Pyridine ,Pivalonitrile ,Organic chemistry ,Acetonitrile ,Molybdenum ,Molecular Structure ,010405 organic chemistry ,Oxides ,Stereoisomerism ,General Chemistry ,0104 chemical sciences ,Dichloroethylenes ,chemistry ,Phosphine - Abstract
Molybdenum complexes with the general formula Mo(NR)(CHR′)(OR″)(Cl)(MeCN) (R = t-Bu or 1-adamantyl; OR″ = a 2,6-terphenoxide) recently have been found to be highly active catalysts for cross-metathesis reactions between Z-internal olefins and Z-1,2-dichloroethylene or Z-(CF3)CH═CH(CF3). In this paper we report methods of synthesizing new potential catalysts with the general formula M(NR)(CHR′)(OR″)(Cl)(L) in which M = Mo or W, NR = N-2,6-diisopropylphenyl or NC6F5, and L is a phosphine, a pyridine, or a nitrile. We also test and compare all catalysts in the cross-metathesis of Z-1,2-dichloroethylene and cyclooctene. Our investigations indicate that tungsten complexes are inactive in the test reaction either because the donor is bound too strongly or because acetonitrile inserts into a W═C bond. The acetonitrile or pivalonitrile Mo(NR)(CHR′)(OR″)(Cl)(L) complexes are found to be especially reactive because the 14e Mo(NR)(CHR′)(OR″)Cl core is accessible through dissociation of the nitrile to a significant e...
- Published
- 2016