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Molybdenum Disubstituted Alkylidene Complexes


Through relatively straightforward techniques that begin with Mo(NAr)(CH-t-Bu)[OCMe(CF3)2]2 (Ar = 2,6-i-Pr2C6H3), we have prepared Mo(NAr)(CMePh)(OMesityl)2, [Mo(NAr)(CMePh)(OC6F5)2]2, Mo(NAr)(CMePh)(OC6F5)2(MeCN), Mo(NAr)(CMePh)(OC6F5)2(bipyridyl), Mo(NAr)(CMePh)(Cl)2(bipyridyl), Mo(NAr)(CMePh)(Cl)(OHMT)(MeCN) (OHMT = O-2,6-(2,4,6-Me3C6H2)2C6H3), and Mo(NAr)(CMePh)(Pyrrolide)(OHMT). X-ray studies reveal that in five compounds the alkylidene isomer (A) is that in which the phenyl group in the alkylidene points toward the imido nitrogen. In Mo(NAr)(CMePh)(OC6F5)2(MeCN) the isomer in which the methyl group points toward the imido nitrogen (isomer B) has cocrystallized with isomer A (12%). In two 14e compounds that contain isomer A, the Mo═C-C angles differ by 30-36°, consistent with a Mo...C-Hβ agostic interaction. Several of the complexes reported here react readily with ethylene, 1-decene, or cyclooctene to give the expected products, thus confirming their viability as initiators or intermediates in metathesis reactions.

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