Quantum-chemical calculations for paramagnetic 13C NMR chemical shifts of iron-bound cyanide ions of iron porphyrins in ground and low-lying excited states containing ferric (dxy)2(dxz,yz)3 and (dxy)1(dxz,yz)4 configurations.

Accurate quantum-chemical calculations were carried out for bis(cyanide) and cyanide-imidazole Fe(III) porphyrins in the ground and low-lying excited states including both the ferric (dxy)2(dxz,yz)3 and (dxy)1(dxz,yz)4 configurations. The trans-ligand effect on the paramagnetic 13C NMR chemical shifts of the iron-bound 13CN- was well reproduced by the present calculations. Further, in bis(cyanide)(meso-tetraethyl) Fe(III) porphyrin, which has a ruffled porphyrin ring, the (dxy)1(dxz,yz)4 configuration is included in the ground state, and the alternative (dxy)2(dxz,yz)3 configuration is located closely in energy to the ground state. Ruffling of porphyrin rings extremely affects the 13C chemical shift of iron-bound CN in the (dxy)1(dxz,yz)4 configuration but not in the (dxy)2(dxz,yz)3 configuration.