Dataset Information

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:Two [Fe(II)(2)(N-EtHPTB)(mu-O(2)X)](2+) complexes, where N-EtHPTB is the anion of N,N,N'N'-tetrakis(2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane and O(2)X is O(2)PPh(2) (1 x O(2)PPh(2)) or O(2)AsMe(2) (1 x O(2)AsMe(2)), have been synthesized. Their crystal structures both show interiron distances of 3.54 A that arise from a (mu-alkoxo)diiron(II) core supported by an O(2)X bridge. These diiron(II) complexes react with O(2) at low temperatures in MeCN (-40 degrees C) and CH(2)Cl(2) (-60 degrees C) to form long-lived O(2) adducts that are best described as (mu-eta(1):eta(1)-peroxo)diiron(III) species (2 x O(2)X) with nu(O-O) approximately 850 cm(-1). Upon warming to -30 degrees C, 2 x O(2)PPh(2) converts irreversibly to a second (mu-eta(1):eta(1)-peroxo)diiron(III) intermediate (3 x O(2)PPh(2)) with nu(O-O) approximately 900 cm(-1), a value which matches that reported for [Fe(2)(N-EtHPTB)(O(2))(O(2)CPh)](2+) (3 x O(2)CPh) (Dong et al. J. Am. Chem. Soc. 1993, 115, 1851-1859). Mossbauer spectra of 2 x O(2)PPh(2) and 3 x O(2)PPh(2) indicate that the iron centers within each species are antiferromagnetically coupled with J approximately 60 cm(-1), while extended X-ray absorption fine structure analysis reveals interiron distances of 3.25 and 3.47 A for 2 x O(2)PPh(2) and 3 x O(2)PPh(2), respectively. A similarly short interiron distance (3.27 A) is found for 2 x O(2)AsMe(2). The shorter interiron distance associated with 2 x O(2)PPh(2) and 2 x O(2)AsMe(2) is proposed to derive from a triply bridged diiron(III) species with alkoxo (from N-EtHPTB), 1,2-peroxo, and 1,3-O(2)X bridges, while the longer distance associated with 3 x O(2)PPh(2) results from the shift of the O(2)PPh(2) bridge to a terminal position on one iron. The differences in nu(O-O) are also consistent with the different interiron distances. It is suggested that the O...O bite distance of the O(2)X moiety affects the thermal stability of 2 x O(2)X, with the O(2)X having the largest bite distance (O(2)AsMe(2)) favoring the 2 x O(2)X adduct and the O(2)X having the smallest bite distance (O(2)CPh) favoring the 3 x O(2)X adduct. Interestingly, neither 3 x O(2)AsMe(2) nor the benzoate analog of 2 x O(2)X (2 x O(2)Bz) are observed.

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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