STRUCTURE AND PRODUCTS OF ELECTROCHEMICAL OXIDATION OF ZIRCONIUM(IV) AND HAFNIUM(IV) BISPORPHYRINATE DOUBLE-DECKERS

被引：45

作者：

BUCHLER, JW ^{[1
]}

DECIAN, A ^{[1
]}

ELSCHNER, S ^{[1
]}

FISCHER, J ^{[1
]}

HAMMERSCHMITT, P ^{[1
]}

WEISS, R ^{[1
]}

机构：

[1] UNIV STRASBOURG 1,CNRS,URA 424,CRISTALLOCHIM & CHIM STRUCT LAB,F-67070 STRASBOURG,FRANCE

来源：

CHEMISCHE BERICHTE-RECUEIL | 1992年 / 125卷 / 01期

关键词：

ZIRCONIUM PORPHYRINS; HAFNIUM PORPHYRINS; PORPHYRIN DOUBLE-DECKERS; METAL BISPORPHYRINATES;

D O I：

10.1002/cber.19921250118

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The electrochemical oxidation of zirconium and hafnium double-deckers M(P)2 (M = Zr, Hf; P = OEP, TPP) (Scheme 1)2) leads to mono- and dications which show near infrared absorption bands which are of almost-equal-to 2000 cm-1 higher energy than those of the corresponding cerium double-decker cations. [Zr(OEP)2]X, [Zr(OEP)2]X2, and [Zr(TPP)2]X (X = ClO4- and PF6-) are isolated after electrochemical oxidation and are characterized by IR and NMR spectroscopy. Magnetic susceptibility measurements (2 K < T < 300 K) of the solids confirm the strong coupling of the electron spins in the diamagnetic dication salt [Zr(OEP)2][ClO4]2. The molecular structure of Zr(OEP)2 is elucidated by an X-ray structural analysis.

引用

页码：107 / 115

页数：9

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