Structural and electron self-exchange rate variations in isomeric (hexaamine)cobalt(III/II) complexes

被引：22

作者：

Bernhardt, PV

Jones, LA

Sharpe, PC

机构：

[1] Department of Chemistry, University of Queensland

来源：

INORGANIC CHEMISTRY | 1997年 / 36卷 / 11期

关键词：

TRANSITION-METAL COMPLEXES; MOLECULAR-MECHANICS; MACROCYCLE 6,13-DIMETHYL-1,4,8,11-TETRAAZACYCLOTETRADECANE-6,13-DIAMINE; TRANSFER REACTIVITY; CRYSTAL-STRUCTURE; COORDINATION; COBALT(III); CIS-6,13-DIMETHYL-1,4,8,11-TETRAAZACYCLOTETRADECANE-6,13-DIAMINE; CHROMIUM(III); COUPLES;

D O I：

10.1021/ic961345e

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The syntheses and characterisation of the new macrocyclic hexaamine trans-(5(S),7(S),12(R),14(R)-tetramethyl)-1,4,8,11-tetraazacyclotetradecane-6,13-diamine (L-6) and its Co-III complex are reported. The X-ray crystal structural analyses of [CoL6]Cl-2(ClO4) [monoclinic, space group C2/c, a = 16.468(3) Angstrom, b = 9.7156(7) Angstrom, c = 15.070(3) Angstrom, beta = 119.431(8)degrees, Z = 4] and the closely related cis-diamino-substituted macrocyclic complex [CoL2](ClO4)(3) . 2H(2)O (L-2 = cis-6,13-dimethyl-1,4,8,11-tetraazacyclotetradecane-6,13-diamine) [orthorhombic, space group Pna2(1), a = 16.8220(8) Angstrom, b = 10.416(2) Angstrom, c = 14.219(3) Angstrom, Z = 4] reveal significant variations in the observed Co-N bond lengths and coordination geometries, which may be attributed to the trans or cis disposition of the pendent primary amines. The Co-III/II self-exchange electron transfer rate constants for these and other closely related hexaamines have been determined, and variations of some 2 orders of magnitude are found between pairs of trans and cis isomeric Co-III complexes.

引用

页码：2420 / 2425

页数：6

共 28 条

[1]

Bauer H.F., 1966, INORG SYNTH, V8, P202

[2]

Bernhardt P., UNPUB

[3] RHODIUM(III) COMPLEXES OF THE AMBIDENTATE MACROCYCLE 6,13-DIAMINO-6,13-DIMETHYL-1,4,8,11-TETRA-AZACYCLOTETRADECANE - CRYSTAL-STRUCTURE OF THE SEXIDENTATE COMPLEX [J].