Wydział Chemii

Lechosław Latos-Grażyński

Krystyna Rachlewicz

Jacek Wojaczyński

1999

Coordination Chemistry Reviews

190-192

109-125

10.1016/S0010-8545(99)00067-3

Naukowa

Angielski

Artykuł

The effects of unconventional modifications of iron tetraarylporphyrins on their electronic structure and chemical properties were examined. The alterations included the β(meso)-substitution or an oxygen atom insertion into an iron–nitrogen bond. The profound transformation of porphyrin to 2-pyridiniumylporphyrin, isoporphyrin or porphodimethene occurred in reactions involving iron porphyrin in highly-oxidized states and pyridine. Addition of 2,4,6-collidine generated iron porphyrin N-oxides. The 2-hydroxy substituted tetraphenylporphyrin (a hybrid-type ligand) coordinates using a tetranitrogen macrocyclic center and an ionized hydroxy group of the periphery to form the cyclic trimer [(2-O–TPP)Fe(III)]₃. The seven pyrrole protons of (2-X-TPP)Fe(III)Cl and [(2-X–TPP)Fe(III)(CN)₂] provided the direct probe of the spin density distribution around the porphyrin macrocycle as determined by ¹H-NMR. Studies on the controlled modification of the tetraarylporphyrin periphery also included a symmetrical modification of a single pyrrole ring to obtain iron(III) quinoxalinoporphyrin characterized by the less common (d_xzd_yz)⁴(d_xy)¹ low-spin ground electronic state of the bis-cyanide derivative [(QTPP)Fe(III)(CN)₂]⁻.

Iron porphyrins, Cation radicals, NMR

https://doi.org/10.1016/S0010-8545(99)00067-3

http://www.elsevier.com