Axial Mn–C_CN Bonds of Cyano Manganese(II) Porphyrin Complexes: Flexible and Weak?

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 (<i>D</i>, <i>E</i>, and <i>E</i>/<i>D</i> (λ)), 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.