Donor-acceptor intermolecular hardness on charge transfer reactions of substituted cobalt phthalocyanines

被引:60
作者
Cárdenas-Jirón, GI [1 ]
Zagal, JH [1 ]
机构
[1] Univ Santiago Chile, Fac Quim & Biol, Dept Quim Mat, Santiago, Chile
来源
JOURNAL OF ELECTROANALYTICAL CHEMISTRY | 2001年 / 497卷 / 1-2期
关键词
donor-acceptor hardness; cobalt phthalocyanines; frontier molecular orbitals; charge transfer reactions;
D O I
10.1016/S0022-0728(00)00434-4
中图分类号
O65 [分析化学];
学科分类号
070302 ; 081704 ;
摘要
We present a theoretical study of the donor-acceptor intermolecular hardness (eta (DA)) associated with the interaction between substituted cobalt phthalocyanines (CoPc(X)(n)) and donors such as molecular oxygen (O-2) or acceptor species such as 2-mercaptoethanol (OHCH2CH2SH), hydrazine (NH2NH2) and hydroxylamine (NH2OH). Semiempirical (PM3) and ab initio (ROHF/ CEP-31G and ROHF/6-31G) theoretical methods were used to determine lit,, for the four charge transfer interactions. Theoretical results of eta (DA) correlate well with rate constants for electro-oxidation of 2-mercaptoethanol, hydrazine and hydroxylamine and for electro-reduction of O-2 for processes occurring on phthalocyanines confined on a graphite electrode. The lower eta (DA) the higher is the reactivity. We also determined the molecular hardness (eta), as defined in density functional theory, of CoPc(X)(n). Linear correlations obtained between eta (DA) and of CoPc(X)(n) for each of the charge transfer reactions studied indicate that the donor-acceptor intermolecular hardness is a reactivity index and possesses a predictive value in determining the catalytic activity of macrocyclic complexes confined on electrode surfaces. (C) 2001 Elsevier Science B.V. All rights reserved.
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页码:55 / 60
页数:6
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