Synthesis and ROMP Chemistry of Decafluoroterphenoxide Molybdenum Imido Alkylidene and Ethylene Complexes

被引：29

作者：

Yuan, Jian ^{[1
]}

Schrock, Richard R. ^{[1
]}

Gerber, Laura C. H. ^{[1
]}

Mueller, Peter ^{[1
]}

Smith, Stacey ^{[1
]}

机构：

[1] MIT, Dept Chem 6 331, Cambridge, MA 02139 USA

来源：

ORGANOMETALLICS | 2013年 / 32卷 / 10期

基金：

美国国家科学基金会;

关键词：

OPENING METATHESIS POLYMERIZATION; MO; PYRROLIDE; EFFICIENT; PRECURSORS; CATALYSTS; METAL;

D O I：

10.1021/om400199u

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

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)(2)C6H3O) and monoarylcodde monopyrrolide (MAP) complexes Mo(NR)(CHCMe2Ph)(Me(2)Pyr)-(OAr) (Me(2)Pyr = 2,S-dimethylpyrrolide; R = C6F3, OAr = DFTO, 2,6dimesitylphenoxide (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)-(CHCMeiPh)(Me(2)Pyr)(HMTO) gives a polymer that contains the expected cis,syndiotactic structure, but polymerization of DCMNBD by Mo(NR)(CHCMe2Ph)(Me(2)Pyr)(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)(DFT0)2 reacts with 3-methyl-3-phenylc-yclopropene (MPCP) to give Mo(NC6F5)(CHCHCMePh)(DFTO)(2) in similar to 50% yield.

引用

页码：2983 / 2992

页数：10

共 38 条

[1] SYNTHESIS, STRUCTURE, AND SPECTROSCOPIC PROPERTIES OF COPPER(II) COMPOUNDS CONTAINING NITROGEN SULFUR DONOR LIGANDS - THE CRYSTAL AND MOLECULAR-STRUCTURE OF AQUA[1,7-BIS(N-METHYLBENZIMIDAZOL-2'-YL)-2,6-DITHIAHEPTANE]COPPER(II) PERCHLORATE [J].