Six-Coordinate Nitrato Complexes of Iron(III) Porphyrins

• Published in: Inorganic chemistry Vol. 47; no. 3; pp. 787 - 789
• Main Authors: Gulyan, Gurgen M, Kurtikyan, Tigran S, Ford, Peter C
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 04.02.2008
• Subjects: Ferric Compounds - chemistry; Isomerism; Nitrates - chemistry; Porphyrins - chemistry; Spectrophotometry, Ultraviolet; Spectroscopy, Fourier Transform Infrared
• ISSN: 0020-1669; 1520-510X
• DOI: 10.1021/ic702102j

The interaction of tetrahydrofuran (THF) with thin films of the nitrato complexes FeIII(Por)(η2-O2NO) [Por = meso-tetraphenylporphyrinato (TPP) and meso-tetratolylporphyrinato (TTP) dianion] at low temperature leads to the formation of the six-coordinate nitrato complex Fe(Por)(THF)(NO3), which was characterized by IR and UV−visible spectroscopies. Formation of the THF adduct was accompanied by nitrate linkage isomerization from bidentate to monodentate coordination. The iron(III) center remains in a high spin state in contrast with the previously observed low-spin nitratonitrosyl complex Fe(TPP)(NO)(η1-ONO2). Upon warming, THF dissociates to restore the initial five-coordinate bidentate nitrato complex.