Synthesis and ROMP Chemistry of Decafluoroterphenoxide Molybdenum Imido Alkylidene and Ethylene Complexes
Author(s)Yuan, Jian; Schrock, Richard Royce; Gerber, Laura C. H.; Muller, Peter; Smith, Stacey
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The bisDFTO alkylidene complexes of molybdenum Mo(NR)(CHCMe2Ph)(DFTO)2 (R = 2,6-i-Pr2C6H3, 2,6-Me2C6H3, C6F5, 1-adamantyl; DFTO = 2,6-(C6F5)2C6H3O) and monoaryloxide monopyrrolide (MAP) complexes Mo(NR)(CHCMe2Ph)(Me2Pyr)(OAr) (Me2Pyr = 2,5-dimethylpyrrolide; R = C6F5, OAr = DFTO, 2,6-dimesitylphenoxide (HMTO); R = 2,6-Me2C6H3, OAr = DFTO) have been prepared in good yields. Addition of dicarbomethoxynorbornadiene (DCMNBD) to bisDFTO complexes yielded polymers that have a cis,isotactic structure. Polymerization of DCMNBD by Mo(NC6F5)(CHCMe2Ph)(Me2Pyr)(HMTO) gives a polymer that contains the expected cis,syndiotactic structure, but polymerization of DCMNBD by Mo(NR)(CHCMe2Ph)(Me2Pyr)(DFTO) (R = C6F5, 2,6-Me2C6H3) generates a polymer that has a cis,isotactic structure, the first observation of a cis,isotactic polymer prepared employing a MAP initiator. Norbornene is polymerized to give what is proposed to be highly tactic cis-polyNBE. Addition of ethylene to Mo(NC6F5)(CHCMe2Ph)(DFTO)2 leads to formation of Mo(NC6F5)(CH2CH2)(DFTO)2, which also behaves as an initiator for polymerization of DCMNBD to cis,isotactic-polyDCMNBD and norbornene to cis highly tactic polyNBE. Mo(NC6F5)(CH2CH2)(DFTO)2 reacts with 3-methyl-3-phenylcyclopropene (MPCP) to give Mo(NC6F5)(CHCHCMePh)(DFTO)2 in 50% yield.
DepartmentMassachusetts Institute of Technology. Department of Chemistry
American Chemical Society
Yuan, Jian, Richard R. Schrock, Laura C. H. Gerber, Peter Müller, and Stacey Smith. “Synthesis and ROMP Chemistry of Decafluoroterphenoxide Molybdenum Imido Alkylidene and Ethylene Complexes.” Organometallics 32, no. 10 (May 24, 2013): 2983–2992.
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