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The two diastereomers of Mo(NAr)(CHCMe(2)Ph)(2,5-dimethylpyrrolide)(1), (S(M)R(1))-2 and (R(M)R(1))-2, respectively, where 1 is an enantiomerically pure (R) phenoxide and Ar = 2,6-diisopropylphenyl, form adducts with PMe(3). One of these ((R(M)R(1))-2(PMe(3))) has been isolated. An X-ray structure reveals that PMe(3) has added trans to the pyrrolide; it is a model for where an olefin would attack the metal. Trimethylphosphine will catalyze slow interconversion of (S(M)R(1))-2 and (R(M)R(1))-2 via formation of weak PMe(3) adducts. Reactions between (S(M)R(1))-2 or (R(M)R(1))-2 and ethylene yield Mo(NAr)(CH(2))(Me(2)Pyr)(1) species in which the configuration at Mo is inverted by ethylene at a rate of the order of the NMR time scale at 22 degrees C via formation of metallacyclobutane intermediates with imido and aryloxide ligands in axial positions. A reactant olefin is proposed to approach Mo and the product olefin to leave Mo trans to the pyrrolide.

Inversion of Configuration at the Metal in Diastereomeric Imido Alkylidene Monoaryloxide Monopyrrolide Complexes of Molybdenum