DFT study of cobalt porphyrin complex for living radical polymerization   of olefins

doi:10.1016/j.comptc.2012.10.010

CORC > 北京大学 > 化学与分子工程学院

	DFT study of cobalt porphyrin complex for living radical polymerization of olefins
	Dong, Huilong ; Hou, Tingjun ; Zhao, Yaguang ; Fu, Xuefeng ; Li, Youyong
刊名	computational and theoretical chemistry
	2012
关键词	Cobalt complexes Living radical polymerization Bond dissociation energy Transition state DFT POLYATOMIC-MOLECULES ORGANIC RADICALS CHAIN TRANSFER VINYL-ACETATE ACRYLATES DENSITY WATER ACID
DOI	10.1016/j.comptc.2012.10.010
英文摘要	We design versatile cobalt porphyrin complexes for living radical polymerization (LRP) of olefins and perform density functional theory (DFT) calculations to investigate the efficiency of cobalt porphyrin complexes. Our calculation results demonstrate that (TMP-OH)Co-R is efficient due to less steric hindrance. By comparing the bond dissociation energies (BDEs) and reaction pathways, our calculation results show that the efficiency of cobalt porphyrin complexes is in the following sequence: (TPFP)Co-R > (TMP-OH)Co-R > (TMP)Co-R. We find that electronic effect and steric hindrance are important for bond dissociation energies of cobalt porphyrin complexes. Among the chosen monomers, Co-C-R BDEs of VAc and AN are the highest, and tBA's is the lowest, which determines their performance in LRP. The polydispersity index (PDI) of these polymerized olefins we obtained is consistent with our calculated BDE. We conclude that the activation barrier of the radical pair correlates with the catalytic efficiency. Low activation barrier corresponds to efficient catalytic reaction. Our results show that the modified species (TMP-OH)Co-II and (TPFP)Coll are better LRP catalysts for olefins than (TMP)Co-II. (C) 2012 Elsevier B.V. All rights reserved.; http://gateway.webofknowledge.com/gateway/Gateway.cgi?GWVersion=2&SrcApp=PARTNER_APP&SrcAuth=LinksAMR&KeyUT=WOS:000312472900009&DestLinkType=FullRecord&DestApp=ALL_WOS&UsrCustomerID=8e1609b174ce4e31116a60747a720701 ; Chemistry, Physical; SCI(E); 6; ARTICLE; 51-59; 1001
语种	英语
内容类型	期刊论文
源URL	[http://ir.pku.edu.cn/handle/20.500.11897/228864]
专题	化学与分子工程学院
推荐引用方式 GB/T 7714	Dong, Huilong,Hou, Tingjun,Zhao, Yaguang,et al. DFT study of cobalt porphyrin complex for living radical polymerization of olefins[J]. computational and theoretical chemistry,2012.
APA	Dong, Huilong,Hou, Tingjun,Zhao, Yaguang,Fu, Xuefeng,&Li, Youyong.(2012).DFT study of cobalt porphyrin complex for living radical polymerization of olefins.computational and theoretical chemistry.
MLA	Dong, Huilong,et al."DFT study of cobalt porphyrin complex for living radical polymerization of olefins".computational and theoretical chemistry (2012).