Axial Mn-C-CN Bonds of Cyano Manganese(II) Porphyrin Complexes: Flexible and Weak?

作者：He, Mingrui; Li, Xiangjun; Liu, Yanhong; Li, Jianfeng^*

来源：Inorganic Chemistry, 2016, 55(12): 5871-5879.

DOI：10.1021/acs.inorgchem.6b00173

• ELECTRON-PARAMAGNETIC-RESONANCE
• INELASTIC NEUTRON-SCATTERING
• NUCLEAR-MAGNETIC-RESONANCE
• ZERO-FIELD SPLITTINGS
• LOW-SPIN
• INTERMOLECULAR INTERACTIONS
• STRUCTURAL-CHARACTERIZATION
• MOLECULAR STEREOCHEMISTRY
• CHLOROFORM SOLVATE
• CRYSTAL-STRUCTURES

Three five-coordinate high-spin (cyano)manganese(II) complexes, utilized tetraphenylporphyrin (TPP), tetratolylporphyrin (TTP), and tetramesitylporphyrin (TMP) as ligands, are prepared and studied by single-crystal X-ray, FT-IR, UV-vis, and EPR spectroscopies. The crystal structure studies revealed noteworthy structural features including unexpectedly wide tilting angles of the axial Mn-C-CN bonds, which is contrasted to the isoelectronic Fe(III)-C-CN bonds. Solid-state EPR measurements (90 K) and simulations are applied to obtain the ZFS parameters (D, E, and E/D (lambda)), which are compared to Mn(II) porphyrin analogues of hemes to understand the ligand field of the cyanide. The solution EPR studies gave new insights into the chemical equilibrium of four- and five-coordinate species, which has been monitored by UV-vis spectroscopy.

• 出版日期2016-6-20
• 单位中国科学院理化技术研究所; 中国科学院大学