五配位锰（II）“栅栏”卟啉配合物的几何结构和电子结构

Geometric and electronic structures of five-coordinate manganese(ii) "picket fence" porphyrin complexes.

作者信息

Yu Qiang, Liu Yanhong, Liu Diansheng, Li Jianfeng

机构信息

Research Institute of Applied Chemistry, Shanxi University, Taiyuan, 030006, China.

出版信息

Dalton Trans. 2015 May 28;44(20):9382-90. doi: 10.1039/c5dt00685f.

DOI:10.1039/c5dt00685f

PMID:25913615

Abstract

Three five-coordinate, high spin manganese(ii) "picket fence" porphyrin complexes, [Mn(TpivPP)(L)] (TpivPP = α,α,α,α-tetrakis(o-pivalamidophenyl)porphyrinato; L = 1-MeIm (1-methylimidazole), 1-EtIm (1-ethylimidazole) and 2-MeHIm (2-methylimidazole)), are synthesized and studied by single-crystal X-ray, UV-vis and electronic paramagnetic resonance (EPR) spectroscopy. Structural parameters are investigated and compared with analogues. Low temperature (90 K), high field EPR studies of [Mn(TpivPP)(1-MeIm)] and [Mn(TpivPP)(2-MeHIm)] showed five resonances including characteristic signals at ∼5.9 and ∼2.0. The simulations of the EPR spectra give the zero field splitting (zfs) parameters (D, E and λ) and the hyperfine coupling constant (A).

摘要

合成了三种五配位、高自旋的锰（II）“栅栏”卟啉配合物[Mn(TpivPP)(L)]（TpivPP = α,α,α,α-四（邻-新戊酰胺基苯基）卟啉；L = 1-MeIm（1-甲基咪唑）、1-EtIm（1-乙基咪唑）和2-MeHIm（2-甲基咪唑）），并通过单晶X射线、紫外可见光谱和电子顺磁共振（EPR）光谱进行了研究。研究了结构参数并与类似物进行了比较。对[Mn(TpivPP)(1-MeIm)]和[Mn(TpivPP)(2-MeHIm)]进行的低温（90 K）、高场EPR研究显示有五个共振峰，包括在~~5.9和~~2.0处的特征信号。EPR光谱的模拟给出了零场分裂（zfs）参数（D、E和λ）以及超精细耦合常数（A）。