期刊
JOURNAL OF ORGANOMETALLIC CHEMISTRY
卷 860, 期 -, 页码 106-116出版社
ELSEVIER SCIENCE SA
DOI: 10.1016/j.jorganchem.2018.02.018
关键词
Titanium; Bidentate ligand; Unsymmetrical N-Heterocyclic carbene; Bis-ligated titanium complex; EthylEne polymerization
资金
- University of Bergen, L. Meltzers Hoyskolefond [2017/3273]
- Norwegian Research Council (FRINATEK) [240333]
Bis-ligated titanium (IV) metal complexes supported by bidentate unsymmetrical o-hydroxyaryl-substituted N-heterocyclic carbene ligands were synthesized and structurally identified. While the direct addition of the doubly deprotonated bulky imidazolidinium chloride salts [Dipp,4-RNHC-H]Cl (with Dipp = 2,6-diisopropylphenyl, R = H (2-hydroxyphenyl), and R = Me (2-hydroxy-4-methyl-phenyl)) with chloro-titanium precursor favors the formation of single stereoisomer corresponding to the bis-ligated titanium complexes trans-([kappa(2)-C,O]-Dipp,4-RNHC)(2)TiCl2 (R = H (2-hydroxyphenyl) for 4a(H), and R = Me (2-hydroxy-4-methyl-phenyl) for 4a(Me)), the reactivity with sterically less hindered imidazolidinium chloride salts [(NHC)-N-Mes,H-H]Cl and [(NHC)-N-Dep,H-H]Cl as protio-ligands (with Mes = 2,4,6-trimethylphenyl and Dep = 2,6-diethylphenyl) did not lead to single stereoisomer, but rearranged into a tetradentate salophen-like complexes cis-([kappa(4)-O,N,N,O]-bis(imidazolidinylidene)TiCl2 as major isomer via presumably the NHCs dimerization from bis-ligated intermediates. These results combined with topographic steric maps as well as the buried volume descriptor (%V-bur) indicate that bidentate bulky N-Dipp-substituted NHC ligands offer some level of steric protection preventing the formation of other possible bis-ligated (C,O)-NHC-titanium stereoisomers and constitutional isomers. (c) 2018 Elsevier B.V. All rights reserved.
作者
我是这篇论文的作者
点击您的名字以认领此论文并将其添加到您的个人资料中。
推荐
暂无数据