DFT Studies on cis-1,4-Polymerization of Dienes Catalyzed by a Cationic Rare-Earth Metal Complex Bearing an Ancillary PNP Ligand
DFT Studies on cis-1,4-Polymerization of Dienes Catalyzed by a Cationic Rare-Earth Metal Complex Bearing an Ancillary PNP Ligand
复制标题
带有辅助 PNP 配体的阳离子稀土金属配合物催化二烯顺式 1,4-聚合的 DFT 研究
作者：
Wang Xingbao;Kang Xiaohui;Zhou Guangli;Qu Jingping;Hou Zhaomin;Luo Yi
Dnsity functional theory (DFT) calculations have been carried out for the highly selective cis-1,4-polymerization of butadiene catalyzed by a cationic rare-earth metal complex bearing an ancillary PNP ligand. It has been found that the chain initiation and propagation of butadiene polymerization occurs via the favorable cis-1,4-insertion route. The trans-1,4 and 1,2-insertion are unfavorable both kinetically and thermodynamically. The chain growth follows the π-allyl-insertion mechanism. The analyses of energy decomposition of transition states indicate that the likelihood of rival insertion pathways is predominantly controlled by the interaction energy of butadiene with a metal center and the deformation energy of butadiene moiety. The electronic factor of the central metal has a decisive influence on the cis- vs. trans-insertion and the regioselectivity (cis-1,4- vs. cis-1,2-insertion) is mainly determined by steric hindrance. Tetrahydrofuran (THF) coordination made monomer insertion less favorable compared with THF-free case and had more noticeable impact on the trans-monomer insertion compared with the cis case. During the chain propagation, cis-insertion of monomer facilitates THF de-coordination and the THF molecule could therefore dissociate from the central metal.
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影响因子：
2.8
作者：
Xiaohui Kang;Guangli Zhou;Xingbao Wang;Jingping Qu;Z. Hou;Yizhan Luo
通讯作者：
Xiaohui Kang;Guangli Zhou;Xingbao Wang;Jingping Qu;Z. Hou;Yizhan Luo
DOI：
10.1002/masy.19930660124
发表时间：
1993-02-01
期刊：
MAKROMOLEKULARE CHEMIE-MACROMOLECULAR SYMPOSIA
影响因子：
--
作者：
WILSON, DJ
通讯作者：
WILSON, DJ
影响因子：
4
作者：
A. Tolpygin;T. A. Glukhova;A. Cherkasov;G. Fukin;D. V. Aleksanyan;Dongmei Cui;A. Trifonov
通讯作者：
A. Tolpygin;T. A. Glukhova;A. Cherkasov;G. Fukin;D. V. Aleksanyan;Dongmei Cui;A. Trifonov
影响因子：
--
作者：
Lixin Zhang;M. Nishiura;M. Yuki;Yi Luo;Z. Hou
通讯作者：
Lixin Zhang;M. Nishiura;M. Yuki;Yi Luo;Z. Hou
影响因子：
2.8
作者：
Xingbao Wang;Feiyue Lin;Jingping Qu;Z. Hou;Yizhan Luo
通讯作者：
Xingbao Wang;Feiyue Lin;Jingping Qu;Z. Hou;Yizhan Luo