1H-NMR and EPR studies of the electronic structure of low-spin ruthenium(III) isocyanide porphyrin complexes:: unusual (dxz,dyz)4 (dxy,)1 configuration

被引：11

作者：

Galardon, E

Le Maux, P

Paul, C

Poriel, C

Simonneaux, G ^{[1
]}

机构：

[1] Univ Rennes 1, Lab Chim Organomet & Biol, CNRS, URA 415, F-35042 Rennes, France

[2] INSA, Grp Rech Chim & Met, F-35043 Rennes, France

来源：

JOURNAL OF ORGANOMETALLIC CHEMISTRY | 2001年 / 629卷 / 1-2期

关键词：

ruthenium porphyrins; isocyanides complexes; paramagnetic complexes; nuclear magnetic resonance;

D O I：

10.1016/S0022-328X(01)00830-0

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis and characterization of the perchlorato derivatives of bis(isocyanide)tetrakis(phenyl)porphynatoruthenium(III) [Ru(TPP)(RNC)(2)]ClO4 (1, R = ' Bu; 2, R = 2,6-xylyl) are reported. The H-1-NMR isotropic shifts at 298 K of the pyrrole protons of the two complexes, varied from -5.44 ppm for 1 to + 2.55 ppm for 2 rather than the expected -31 ppm, based on previously studied aryl complexes of low-spin ruthenium porphyrins. The EPR spectrum of 2 in solution is axial, with g(perpendicular to) = 2.07 and g(II) = 1.99 at 4 K, Sigmag(2) = 12.53. These spectroscopic observations are indicative of a metal-based electron for complex with a (d(xz), d(yz))(4) (d(xy))(1) ground state at any temperature. (C) 2001 Elsevier Science B.V. All rights reserved.

引用

页码：145 / 152

页数：8

共 43 条

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