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).
Cheng
Ru-Jen
RJ
Department of Chemistry, National Chung-Hsing University, Taichung, Taiwan, Republic of China. rjcheng@mail.nchu.edu.tw
Lee
Chang-Hung
CH
Chao
Chia-Wei
CW