五配位钴(III)的中间(S = 1)自旋态：N-邻羟基苯甲酰胺-中四苯基卟啉钴(III)，Co(N-NCO(o-O)C6H4-tpp)的磁性性质。

Intermediate (S = 1) spin state in five-coordinate cobalt(III): magnetic properties of N-o-hydroxy-benzamido-meso-tetraphenylporphyrin cobalt(III), Co(N-NCO(o-O)C6H4-tpp).

机构信息

Department of Chemistry, National Chung Hsing University, Taichung, 40227, Taiwan.

出版信息

Dalton Trans. 2010 Mar 14;39(10):2609-14. doi: 10.1039/b919686b. Epub 2010 Jan 27.

DOI:10.1039/b919686b

PMID:20179854

Abstract

The crystal structures of paramagnetic N-o-oxido-benzimido-meso-tetraphenylporphyrinato (-kappa(4),N(1),N(2),N(3),N(5),kappaO(2))cobalt(III) [Co(N-NCO(o-O)C(6)H(4)-tpp); 2] (S = 1) and diamagnetic N-o-oxido-benzimido-meso-tetraphenylporphyrinato (-kappa(4),N(1),N(2),N(3),N(5),kappaO(2)) gallium(III) chloroform.methanol solvate [Ga(N-NCO(o-O)C(6)H(4)-tpp).0.5CHCl(3).MeOH; 3.0.5CHCl(3).MeOH] (S = 0) were determined. The coordination sphere around Co(III) in 2 [or Ga(III) in 3.0.5CHCl(3).MeOH] is described as five-coordinate distorted trigonal bipyramid (DTBP) with O(1), N(1) and N(3) [or O(2), N(1), N(3)] lying in the equatorial plane for 2 [or 3.0.5CHCl(3).MeOH]. The magnitude of axial (D) zero-field splitting (ZFS) for the Co(III) (S = 1) in 2 was determined as approximately 107 cm(-1) by paramagnetic susceptibility measurements. The compound (2) reacts in donor solvent such as pyridine to form six-coordinate diamagnetic species of the type Co(N-NCO(o-O)C(6)H(4)-tpp)(py) (4), whose (1)H NMR spectra can be interpreted as for Co(III) in an octahedral environment.

摘要

顺磁的 N-邻-氧代-苯并亚氨基-间-四苯基卟啉（-κ(4),N(1),N(2),N(3),N(5),κO(2))钴(III) [Co(N-NCO(o-O)C(6)H(4)-tpp); 2]（S = 1）和反磁的 N-邻-氧代-苯并亚氨基-间-四苯基卟啉（-κ(4),N(1),N(2),N(3),N(5),κO(2))镓(III)三氯甲烷.甲醇溶剂化物[Ga(N-NCO(o-O)C(6)H(4)-tpp).0.5CHCl(3).MeOH; 3.0.5CHCl(3).MeOH]（S = 0）的晶体结构已被确定。在 2 中，钴(III)的配位球[或 3.0.5CHCl(3).MeOH 中的 Ga(III)]被描述为五配位的扭曲三角双锥（DTBP），其中 O(1)、N(1)和 N(3)[或 O(2)、N(1)、N(3)]位于赤道平面上。2 [或 3.0.5CHCl(3).MeOH]。通过顺磁磁化率测量，确定了 2 中钴(III)（S = 1）的轴向（D）零场分裂（ZFS）的大小约为 107 cm(-1)。该化合物（2）在供体溶剂（如吡啶）中反应，形成六配位的反磁性物种 Co(N-NCO(o-O)C(6)H(4)-tpp)(py)（4），其（1）H NMR 谱可以解释为八面体环境中的 Co(III)。