咔咯锰(Ⅲ)与锰(V)-氧配合物与含氮配体的轴向配位性质

引用本文: 龚丽珍, 徐志广, 许旋, 何婧, 王琦, 刘海洋. 咔咯锰(Ⅲ)与锰(V)-氧配合物与含氮配体的轴向配位性质[J]. 物理化学学报, 2014, 30(2): 265-272. doi: 10.3866/PKU.WHXB201312181 shu

Citation: NG Li-Zhen, XU Zhi-Guang, XU Xuan, HE Jing, WANG Qi, LIU Hai-Yang. Axial Coordination Behavior of Corrole Mn^Ⅲ and Mn^VO Complexes with N-Based Ligands[J]. Acta Physico-Chimica Sinica, 2014, 30(2): 265-272. doi: 10.3866/PKU.WHXB201312181 shu

咔咯锰(Ⅲ)与锰(V)-氧配合物与含氮配体的轴向配位性质

龚丽珍 ^1, ,
徐志广 ^1, ,
许旋 ^1, ,
何婧 ^1, ,
王琦 ^2, ,
刘海洋 ^2,

基金项目:
国家自然科学基金(21171057，21371059) (21171057，21371059)

广东省自然科学基金(S2012010008763)资助项目 (S2012010008763)

摘要:

采用密度泛函理论(DFT)的BP86方法对含氮配体咪唑、甲基咪唑、异丙基咪唑和吡啶与5,10,15-三(五氟苯基)咔咯锰[(TPFC)Mn^Ⅲ]和5,10,15-三(五氟苯基)咔咯锰氧[(TPFC)Mn^VO]的轴向配位性质进行理论研究.计算结果表明配体能与五重态下的(TPFC)Mn^Ⅲ形成有效的轴向配位作用，结合能绝对值次序为：咪唑>4-甲基咪唑>吡啶，与实验结果一致. 另外，结合能和轴向配位键长数据显示，这些配体不能与基态(单重态)或三重态(TPFC)Mn^VO中的Mn^V原子形成有效的轴向配位作用，自然键轨道(NBO)分析表明其Mn^V没有空的3d 轨道来接受配体的孤对电子，但配体可与三重态下的(TPFC)Mn^VO形成弱的配位作用.

关键词:

English

Axial Coordination Behavior of Corrole Mn^Ⅲ and Mn^VO Complexes with N-Based Ligands

1.
1 Key Laboratory of Theoretical Chemistry of Environment, Ministry of Education, School of Chemistry and Environment, South China Normal University, Guangzhou 510006, P. R. China;
2 Department of Chemistry, South China University of Technology, Guangzhou 510641, P. R. China
Received Date: 08 October 2013
Available Online: 23 January 2014
Fund Project:
国家自然科学基金(21171057，21371059)

广东省自然科学基金(S2012010008763)资助项目

Abstract:

The axial coordination behavior of the 5,10,15-tris(pentafluorophenyl)corrole manganese [(TPFC)Mn^Ⅲ] and 5,10,15-tris(pentafluorophenyl)corrole manganese(V)-oxo [(TPFC)Mn^VO] complexes with N-based ligands, such as imidazole, methylimidazole, isopropylimidazole, and pyridine, were investigated using density functional theory (DFT) at BP86 level. The results show these N-based ligands can form a stable axial coordination complex with (TPFC)Mn^Ⅲ in its quintet state. The coordination binding strength followed the order imidazole>4-methylimidazole>pyridine, which is in agreement with experimental results. The binding energy and the large distance between the Mn and N atom of the ligands indicates that (TPFC)Mn^VO cannot form an effective coordination bond in its singlet or triple state. Natural bond orbital (NBO) analysis indicates that the 3d orbitals of the Mn atom in (TPFC)Mn^VO are fully occupied, and there are no empty 3d orbitals to accept lone pair electrons from the ligands. However, there is a weak coordination interaction between the ligands and (TPFC)Mn^VO in its triplet state.

Key words:

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沈阳化工大学材料科学与工程学院沈阳 110142

咔咯锰(Ⅲ)与锰(V)-氧配合物与含氮配体的轴向配位性质

English

Axial Coordination Behavior of Corrole Mn^Ⅲ and Mn^VO Complexes with N-Based Ligands

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

咔咯锰(Ⅲ)与锰(V)-氧配合物与含氮配体的轴向配位性质

English

Axial Coordination Behavior of Corrole MnⅢ and MnVO Complexes with N-Based Ligands

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

Axial Coordination Behavior of Corrole Mn^Ⅲ and Mn^VO Complexes with N-Based Ligands

CCS Chemistry：颜徐州、鲍哲南：你的皮肤可能是一片SPMs