title: Electronic structure of iron chlorins: characterization of bis(l-valine methyl ester)(meso-tetraphenylchlorin)iron(III)triflate and bis(l-valine methyl ester)(meso-tetraphenylchlorin)iron(II).
abstract: The synthesis and characterization of the two iron chlorin complexes [Fe(III)(TPC)(NH(2)CH(CO(2)CH(3))(CH(CH(3))(2)))(2)]CF(3)SO(3) (1) and Fe(II)(TPC)[(NH(2)CH(CO(2)CH(3))(CH(CH(3))(2))](2) (2) are reported. The crystal structure of complex 1 has been determined. The X-ray structure shows that the porphyrinate rings are weakly distorted. The metal-nitrogen distances to the reduced pyrrole N(4), 2.034(4) A, and to the pyrrole trans to it N(2), 2.012(4) A, are longer than the distances to the two remaining nitrogens [N(1), 1.996(4) A, and N(3), 1.984(4) A], leading to a core-hole expansion of the macrocycle due to the reduced pyrrole. The (1)H NMR isotropic shifts at 20 degrees C of the different pyrrole protons of 1 varied from -0.8 to -48.3 ppm according to bis-ligated complexes of low-spin ferric chlorins. The EPR spectrum of [Fe(TPC)(NH(2)CH(CO(2)CH(3))(CH(CH(3))(2)))(2)]CF(3)SO(3) (1) in solution is rhombic and gives the principal g values g(1) = 2.70, g(2) = 2.33, and g(3) = 1.61 (Sigmag(2) = 15.3). These spectroscopic observations are indicative of a metal-based electron in the d(pi) orbital for the [Fe(TPC)(NH(2)CH(CO(2)CH(3))(CH(CH(3))(2)))(2)]CF(3)SO(3) (1) complex with a (d(xy))(2)(d(xz)d(yz))(3) ground state at any temperature. The X-ray structure of the ferrous complex 2 also shows that the porphyrinate rings are weakly distorted. The metal-nitrogen distances to the reduced pyrrole N(4), 1.991(5) A, and to the pyrrole trans to it N(2), 2.005(6) A, are slightly different from the distances to the two remaining nitrogens [N(1), 1.988(5) A, and N(3), 2.015(5) A], leading to a core-hole expansion of the macrocycle due to the reduced pyrrole.
authors.affiliation: Laboratoire de Chimie Organométallique et Biologique, UMR CNRS 6509, Université de Rennes 1, Campus de Beaulieu, 35042 Rennes Cedex, France. simonnea@univ-rennes1.fr
authors.forename: Gérard
authors.initials: G
authors.lastname: Simonneaux
authors.forename: Marwan
authors.initials: M
authors.lastname: Kobeissi
authors.forename: Loîc
authors.initials: L
authors.lastname: Toupet
mesh_terms: D018360:Crystallography, X-Ray; D004578:Electron Spin Resonance Spectroscopy; D007501:Iron / Q000737:chemistry*; D008024:Ligands; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D015394:Molecular Structure; D009942:Organometallic Compounds / Q000138:chemical synthesis*; D011166:Porphyrins / Q000737:chemistry*; D013237:Stereoisomerism; D014633:Valine / Q000737:chemistry*
chemical_list: D008024:Ligands; D009942:Organometallic Compounds; D011166:Porphyrins; C006969:chlorin; D007501:Iron; D014633:Valine