The effect of ligand charge on the coordination geometry of an Fe(III) ion: Five- and six-coordinate Fe(III) complexes of tris(2-benzimidazolylmethyl)amine
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- The effect of ligand charge on the coordination geometry of an Fe(III) ion: Five- and six-coordinate Fe(III) complexes of tris(2-benzimidazolylmethyl)amine
- Moon, D; Lah, Myoung Soo; Del Sesto, RE; Miller, JS
- BINUCLEAR IRON(III) COMPLEX; MAGNETIC-PROPERTIES; CRYSTAL-STRUCTURE; MU-OXO; SUPEROXIDE-DISMUTASE; MOLECULAR-STRUCTURE; TRIPODAL LIGAND; TRIS(IMIDAZOLYLMETHYL)AMINE LIGANDS; NITRILE HYDRATASE; DIIRON COMPLEXES
- Issue Date
- AMER CHEMICAL SOC
- INORGANIC CHEMISTRY, v.41, no.18, pp.4708 - 4714
- By using the tripodal tetradentate ligand tris(2-benzimidazolylmethyl)amine (H(3)ntb), which can have several charge states depending on the number of secondary amine protons, mononuclear octahedral and dinuclear trigonal bipyramidal Fe(III) complexes were prepared. The reaction of mononuclear octahedral [FeIII(H(3)ntb)Cl-2]ClO4, 1, with 3 equiv of sec-butylamine in methanol led to the formation of mononuclear cis-dimethoxo octahedral Fe-III(H(2)ntb)(OMe)(2), 2. One equivalent of the sec-butylamine was used to generate the monoanionic H(2)ntb(-) ligand where one of the three amines in the benzimidazolyl groups was deprotonated. The remaining 2 equiv were used to generate two methoxides that were coordinated to the octahedral Fe(III) ion in a cis fashion as demonstrated by the chlorides in 1. Reaction of 1 with excess (7 equiv) sec-butylamine generated the doubly deprotonated dianionic Hntb(2-) that stabilized the dinuclear mu-oxo (Fe2O)-O-III(Hntb)(2), 3, adopting a five-coordinate trigonal bipyramidal geometry. The magnetic data for 3 are consistent with the antiferromagnetically coupled Fe-III (S = 5/2) sites with the coupling constant J = -127 cm(-1).
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