A MOLECULAR-ORBITAL APPROACH TO COLIGAND ISOMER FORMATION

被引：5

作者：

BOCA, R

HVASTIJOVA, M

KOHOUT, J

机构：

[1] Department of Inorganic Chemistry, Slovak Technical University

来源：

JOURNAL OF COORDINATION CHEMISTRY | 1994年 / 33卷 / 02期

关键词：

COLIGAND ISOMERISM; QUASI-RELATIVISTIC INDO CALCULATIONS; COPPER(II); ISOCYANATE; DIMETHYLPYRAZOLE;

D O I：

10.1080/00958979408024272

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Coligand isomerism is exemplified by a pair of [Cu(dMPZ)2(NCO)2] and [Cu(dmpz.NCO)2] complexes (dmpz = 3,5-dimethylpyrazole). The former isomer (I) contains dmpz and NCO- ligands whereas the latter (II) consists of 1-carbamoyl-3,5-dimethylpyrazolate anions chelated to the copper(II) central atom. This new ligand is formed by nucleophilic addition of the dmpz ligand to the cyanate group in the Cu(II) coordination sphere. The cyanate complex transforms under heating to the more stable isomer II. On the contrary, isomer II disolves in DMSO and DMF and its counterpart I is formed. A molecular-orbital study (quasirelativistic INDO/1 method) rationalizes this behaviour and maps the reaction path of the hydrogen transfer over the molecular skeleton.

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页码：137 / 145

页数：9

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