505053-22-5Relevant articles and documents
Synthesis and ROMP chemistry of decafluoroterphenoxide molybdenum imido alkylidene and ethylene complexes
Yuan, Jian,Schrock, Richard R.,Gerber, Laura C. H.,Mueller, Peter,Smith, Stacey
, p. 2983 - 2992 (2013/06/27)
The bisDFTO alkylidene complexes of molybdenum Mo(NR)(CHCMe 2Ph)(DFTO)2 (R = 2,6-i-Pr2C6H 3, 2,6-Me2C6H3, C6F 5, 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(NC 6F5)(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)(CH 2CH2)(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)(CH 2CH2)(DFTO)2 reacts with 3-methyl-3- phenylcyclopropene (MPCP) to give Mo(NC6F5)(CHCHCMePh) (DFTO)2 in ～50% yield.
