Antiferromagnetic coupling in a six-coordinate high spin cobalt(II)-semiquinonato complex

被引：78

作者：

Caneschi, A ^{[1
]}

Dei, A ^{[1
]}

Gatteschi, D ^{[1
]}

Tangoulis, V ^{[1
]}

机构：

[1] Univ Florence, Dept Chem, I-50121 Florence, Italy

来源：

INORGANIC CHEMISTRY | 2002年 / 41卷 / 13期

关键词：

D O I：

10.1021/ic020243n

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The 3,5-di-tert-butyl-catecholato and 9,10-phenanthrenecatecholato adducts of the cobalt-tetraazamacrocycle complex Co(Me(4)CYClaM)(2+) (Me(4)CYClam = 1, 4,8,11-tetramethyl-1,4,8, 11-tetraazacyclotetradecane) were synthesized and oxidized. The oxidation reaction products were isolated in the solid state as hexafluorophosphate derivatives. Both these complexes can be formulated as 1:1 cobalt(II)-semiquinonato complexes, that is, Co(Me(4)CYClam)(DBSQ)PF6 (1) and Co(Me(4)CYclam)(PhSQ)PF6 (2), in the temperature range 4-300 K, in striking contrast with the charge distribution found in similar adducts formed by related tetraazamacrocycles, The synthesis strategy and the structural, spectroscopic, and magnetic properties are reported and discussed, The crystallographic data for 2 are as follows: monoclinic, space group P2(1)/a, no. 14, a = 14.087(4) Angstrom, b = 15.873(4) Angstrom, c = 14.263 (7) Angstrom, alpha = 89.91(3)degrees, beta = 107.34(2)degrees, gamma = 90,08(2)degrees, Z = 4, Both these complexes are characterized by triplet electronic ground states arising from the antiferromagnetic coupling between the high-spin d(7) metal ion and the radical ligand.

引用

页码：3508 / 3512

页数：5

共 48 条

[1]

ABAKUMOV GA, 1993, DOKL AKAD NAUK, V328, P12

[2] Density functional study of the valence-tautomeric interconversion low-spin [Co-III(SQ)(Cat)(phen)] reversible arrow high-spin [Co-II(SQ)(2)(phen)] [J].