Synthesis of Methylidene Complexes that Contain a 2,6-Dimesitylphenylimido Ligand and Ethenolysis of 2,3-Dicarbomethoxynorbornadiene

被引：19
作者：
Gerber, Laura C. H. [1 ]
Schrock, Richard R. [1 ]
机构：
[1] MIT, Dept Chem 6 331, Cambridge, MA 02139 USA
来源：
ORGANOMETALLICS | 2013年 / 32卷 / 19期
基金：
美国国家科学基金会;
关键词：
RING-OPENING/CROSS-METATHESIS; SELECTIVE OLEFIN METATHESIS; PYRROLIDE MAP COMPLEXES; ALKYLIDENE COMPLEXES; CROSS-METATHESIS; NORBORNENE DERIVATIVES; RUTHENIUM CATALYSTS; CLOSING METATHESIS; AROMATIC RING; ENOL ETHERS;
D O I：
10.1021/om400844k
中图分类号：
O61 [无机化学];
学科分类号：
070301 ; 081704 ;
摘要：
Monoalkoxide pyrrolide (MAP) complexes that contain a 2,6-dimesitylphenylimido (NAr*) ligand react with ethylene to yield unsubstituted metallacyclobutanes that are in equilibrium with methylidene complexes, W(NAr*)(CH2)(Me(2)Pyr)(OR) (R = t-Bu, OCMe(CF3)(2), SiPh3, or 2,6-Me2C6H3). Polymerization of 2,3-dicarbomethoxynorbomadiene (DCMNBD) with M=CHCMe2Ph (M = Mo or W) initiators is slow as a consequence of a slow propagation step. However, W(NAr*)(CH2)(Me(2)Pyr)(OR) (R = SiPh3 or 2,6-dimethylphenyl) complexes react readily with 1 equiv of DCMNBD to give a monoinsertion product. The facile reaction between the monoinsertion product and ethylene then allows these complexes to be catalyts for the ring-opening cross-metathesis (ethenolysis) of DCMNBD and DCMNBE (2,3-dicarbomethoxynorbornene) with minimal formation of polymer.
引用
收藏
页码：5573 / 5580
页数：8
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