An unexpected bonding interaction between d(xy) and axial cyanide mediated by porphyrin deformation.

Through density functional calculation and NMR spectroscopy, an unexpected bonding interaction between d(xy) and axial cyanides is revealed to account for the lower shielding of axial cyanide of ruffled [Fe(TRP)(CN)(2)](-) complexes with the contribution of the unusual low-spin electronic structure (d(xz)d(yz))(4)(d(xy))(1).