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Titolo:
H-1 NMR and EPR studies of the electronic structure of low-spin iron(III) isocyanide mesotetraphenylchlorin complexes: a (d(xz),d(yz))(4)(d(xy))(1) configuration from 293 to 4 K
Autore:
Simonneaux, G; Kobeissi, M;
Indirizzi:
Univ Rennes 1, Lab Chim Organomet & Biol, CNRS, UMR 6509, F-35042 Rennes, France Univ Rennes 1 Rennes France F-35042 RS, UMR 6509, F-35042 Rennes, France
Titolo Testata:
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS
fascicolo: 10, , anno: 2001,
pagine: 1587 - 1592
SICI:
1472-7773(2001):10<1587:HNAESO>2.0.ZU;2-Z
Fonte:
ISI
Lingua:
ENG
Soggetto:
RESONANCE RAMAN-SPECTROSCOPY; NUCLEAR MAGNETIC-RESONANCE; AXIAL LIGATION EQUILIBRIA; D TERMINAL OXIDASE; PROSTHETIC GROUP; CHLORIN COMPLEXES; ESCHERICHIA-COLI; HEME-PROTEINS; CYTOCHROME-D; PROTON NMR;
Tipo documento:
Article
Natura:
Periodico
Settore Disciplinare:
Physical, Chemical & Earth Sciences
Citazioni:
59
Recensione:
Indirizzi per estratti:
Indirizzo: Simonneaux, G Univ Rennes 1, Lab Chim Organomet & Biol, CNRS, UMR 6509, F-35042 Rennes, France Univ Rennes 1 Rennes France F-35042 F-35042 Rennes, France
Citazione:
G. Simonneaux e M. Kobeissi, "H-1 NMR and EPR studies of the electronic structure of low-spin iron(III) isocyanide mesotetraphenylchlorin complexes: a (d(xz),d(yz))(4)(d(xy))(1) configuration from 293 to 4 K", J CHEM S DA, (10), 2001, pp. 1587-1592

Abstract

Reaction of (tetraphenylchlorinato)iron(III) chloride with eight equivalents of tert-butyl isocyanide and 2,6-xylyl isocyanide in the presence of zinc amalgam afforded Fe(TPC)(t-BuNC)(2) 1 and Fe(TPC)(2,6-xylylNC)(2) 2, respectively. The synthesis and characterization of the trifluoromethanesulfonato derivatives of (tetraphenylchlorinato)iron(III) 3, bis(tert-butyl isocyanide)(tetraphenylchlorinato)iron(III) 4, and bis(2,6-xylyl isocyanide)(tetraphenylchlorinato)iron(III) 5 are reported: [Fe(TPC)]CF3SO3 3, [Fe(TPC)(t-BuNC)(2)] CF3SO3 4 and [Fe(TPC)(2,6-xylylNC)(2)]CF3SO3 5. The H-1 NMR isotropic shifts at 20 degreesC of the pyrrole protons of the two complexes 4 and5, varied from 5 ppm for 4 to 8 ppm for 5 rather than the expected -10 to -30 ppm, based on previously studied bis-ligated complexes of low-spin iron(III) chlorins. EPR spectra of [Fe(TPC)(t-BuNC)(2)]CF3SO3 4 in solution areaxial, with g(perpendicular to)=2.15 and g(parallel to)=1.97 at 4 K, Sigmag(2)=14.7. All physical properties are consistent with a low-spin iron(III)with an unusual ground-state configuration (d(xz),d(yz))(4)(d(xy))(1).

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Documento generato il 31/03/20 alle ore 22:36:11