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Metal‐Porphyrin Orbital Interactions in Paramagnetic Iron Complexes Having Planar and Deformed Porphyrin Ring
Author(s) -
Nakamura Mikio,
Ikezaki Akira,
Takahashi Masashi
Publication year - 2013
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201200474
Subject(s) - porphyrin , chemistry , atomic orbital , paramagnetism , crystallography , molecular orbital , chemical shift , metal , ring (chemistry) , heme , molecule , carbon fibers , photochemistry , organic chemistry , electron , condensed matter physics , quantum mechanics , composite number , physics , materials science , composite material , enzyme
1 H and 13 C NMR chemical shifts of iron porphyrin complexes are determined mainly by the spin densities at the peripheral carbon and nitrogen atoms caused by the interaction between paramagnetic iron 3d and porphyrin molecular orbitals. This review describes how the half‐occupied iron 3d orbitals such as d π (d xz , d yz ), d xy , d z 2, and d x 2‐ y 2interact with a specific porphyrin molecular orbital and affect the 1 H and 13 C NMR chemical shifts in planar, ruffled, saddled, and domed complexes. Revealing the relationship between the orbital interactions and NMR chemical shifts is quite important to determine the fine electronic structures of synthetic iron porphyrin complexes as well as naturally occurring heme proteins.