Comparison of o-benzoquinonediimine with bipyridine and bipyrazine in electronic coupling to ruthenium(II), as a function of spectator ligand

被引:69
作者
Lever, ABP [1 ]
Gorelsky, SI [1 ]
机构
[1] York Univ, Dept Chem, Toronto, ON M3J 1P3, Canada
关键词
pi-acceptor; sigma-electron; o-benzoquinonediimine; ZINDO; semi-empirical calculations; electronic spectra;
D O I
10.1016/S0010-8545(00)00253-8
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
When comparing [Ru(LL)(3)](2+) with [Ru(NH(3))(4)(LL)](2+), the question is raised whether the replacement of the relatively poor LL (LL = 2,2'-bipyridine, 2,2'-bipyrazine or o-benzoquinonediimine) pi-acceptor and sigma-electron ligands by the o-electron rich ammonia ligands permits a significant improvement in coupling/pi-back donation to the remaining LL. Using a ZINDO analysis of the electronic structures of these species, it is shown that 2,2'-bipyridine is unable to accept the extra electron density from the ruthenium center, while o-benzoquinonediimine can readily do so. The ligand 2,2'-bipyrazine is slightly more able to accept the electron density than 2,2'-bipyridine, (C) 2000 Elsevier Science S.A. All rights reserved.
引用
收藏
页码:153 / 167
页数:15
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