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A Sulfide-Bridged Diiron(II) Complex with a cis-N2H4Ligand.

ABSTRACT: A sulfide-bridged diiron(II) complex bearing a cis-N2H4 (hydrazine) ligand has been prepared by reaction of LFeII(?-S)FeIIL (1; L = sterically encumbered ?diketiminate ligand) with 2 molar equivalents of N2H4. The metastable diiron(II) hydrazine complex LFeII(?-S)(?H N-NH2)FeII (3) is formed, as shown by crystallography, and NMR, vibrational, and electronic absorption spectroscopies. Compound 3 has been crystallographically characterized as its DBU (1,8-diazabicyclo[5.4.0]undec-7$ene) adduct, which exhibits weak N-H···DBU hydrogen bonding. The synthetic process evolves roughly 2 equivalents of NH3. The cis-N2H4 bridge in 3 may be relevant to the structure and function of intermediates on the FeMoco of nitrogenase.

SUBMITTER: Stubbert BD

PROVIDER: S-EPMC3963182 | biostudies-literature | 2013 Jul

REPOSITORIES: biostudies-literature

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A Sulfide-Bridged Diiron(II) Complex with a cis-N2H4Ligand.

Stubbert Bryan D BD Vela Javier J Brennessel William W WW Holland Patrick L PL

Zeitschrift fur anorganische und allgemeine Chemie 20130701 8-9

A sulfide-bridged diiron(II) complex bearing a cis-N2H4 (hydrazine) ligand has been prepared by reaction of LFeII(μ-S)FeIIL (1; L = sterically encumbered βdiketiminate ligand) with 2 molar equivalents of N2H4. The metastable diiron(II) hydrazine complex LFeII(μ-S)(μH N-NH2)FeII (3) is formed, as shown by crystallography, and NMR, vibrational, and electronic ...[more]

PMID: 24678131

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Project description:A dinucleating macrocycle, H(2)PIM, containing phenoxylimine metal-binding units has been prepared. Reaction of H(2)PIM with [Fe(2)(Mes)(4)] (Mes = 2,4,6-trimethylphenyl) and sterically hindered carboxylic acids, Ph(3)CCO(2)H or Ar(Tol)CO(2)H (2,6-bis(p-tolyl)benzoic acid), afforded complexes [Fe(2)(PIM)(Ph(3)CCO(2))(2)] (1) and [Fe(2)(PIM)(Ar(Tol)CO(2))(2)] (2), respectively. X-ray diffraction studies revealed that these diiron(II) complexes closely mimic the active site structures of the hydroxylase components of bacterial multicomponent monooxygenases (BMMs), particularly the syn disposition of the nitrogen donor atoms and the bridging μ-η(1)η(2) and μ-η(1)η(1) modes of the carboxylate ligands at the diiron(II) centers. Cyclic voltammograms of 1 and 2 displayed quasi-reversible redox couples at +16 and +108 mV vs ferrocene/ferrocenium, respectively. Treatment of 2 with silver perchlorate afforded a silver(I)/iron(III) heterodimetallic complex, [Fe(2)(μ-OH)(2)(ClO(4))(2)(PIM)(Ar(Tol)CO(2))Ag] (3), which was structurally and spectroscopically characterized. Complexes 1 and 2 both react rapidly with dioxygen. Oxygenation of 1 afforded a (μ-hydroxo)diiron(III) complex [Fe(2)(μ-OH)(PIM)(Ph(3)CCO(2))(3)] (4), a hexa(μ-hydroxo)tetrairon(III) complex [Fe(4)(μ-OH)(6)(PIM)(2)(Ph(3)CCO(2))(2)] (5), and an unidentified iron(III) species. Oxygenation of 2 exclusively formed di(carboxylato)diiron(III) compounds, a testimony to the role of the macrocylic ligand in preserving the dinuclear iron center under oxidizing conditions. X-ray crystallographic and (57)Fe Mössbauer spectroscopic investigations indicated that 2 reacts with dioxygen to give a mixture of (μ-oxo)diiron(III) [Fe(2)(μ-O)(PIM)(Ar(Tol)CO(2))(2)] (6) and di(μ-hydroxo)diiron(III) [Fe(2)(μ-OH)(2)(PIM)(Ar(Tol)CO(2))(2)] (7) units in the same crystal lattice. Compounds 6 and 7 spontaneously convert to a tetrairon(III) complex, [Fe(4)(μ-OH)(6)(PIM)(2)(Ar(Tol)CO(2))(2)] (8), when treated with excess H(2)O.

Dataset Information

A Sulfide-Bridged Diiron(II) Complex with a cis-N2H4Ligand.

Publications

A Sulfide-Bridged Diiron(II) Complex with a <i>cis</i>-N<sub>2</sub>H<sub>4</sub>Ligand.

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