Iron-sulfur-carbonyl and -nitrosyl complexes: A laboratory experiment

Glidewell, Christopher; Hyde, Andrew; McKechnie, James S.; Pogorzelec, Peter J.

doi:10.1021/ed062p534

Cited by 5 publications

(3 citation statements)

References 15 publications

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“…Although dinuclear iron nitrosyl complexes are known, they contain phosphine, thiolate, , or sulfide , ligands. Surprisingly, no synthetic carboxylate-bridged non-heme diiron analogs of Hr or R2 have been reported that mimic the NO binding ability of these proteins.…”

Section: Introductionmentioning

confidence: 99%

“…To circumvent this problem, the notation {MNO} x has been adopted, where x represents the sum of the electrons in the metal d and NO π* orbitals. 14 Although dinuclear iron nitrosyl complexes are known, they contain phosphine, 18 thiolate, 19,20 or sulfide 21,22 ligands. Surprisingly, no synthetic carboxylate-bridged non-heme diiron analogs of Hr or R2 have been reported that mimic the NO binding ability of these proteins.…”

Section: Introductionmentioning

confidence: 99%

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A Carboxylate-Bridged Non-Heme Diiron Dinitrosyl Complex

1996

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The reaction of nitric oxide with the carboxylate-bridged diiron(II) complex [Fe(2)(Et-HPTB)(O(2)CPh)](BF(4))(2) (1a) afforded the dinitrosyl adduct, [Fe(2)(NO)(2)(Et-HPTB)(O(2)CPh)](BF(4))(2) (1b), where Et-HPTB = N,N,N',N'-tetrakis(N-ethyl-2-benzimidazolylmethyl)-2-hydroxy-1,3-diaminopropane, in 69% yield. Compound 1b further reacts with dioxygen to form the bis(nitrato) complex, [Fe(2)(Et-HPTB)(NO(3))(2)(OH)](BF(4))(2) (1c). The structure of 1b was determined by X-ray crystallography (triclinic, P&onemacr;, a = 13.5765(8) Å, b = 15.4088(10) Å, c = 16.2145(10) Å, alpha = 73.656(1) degrees, beta = 73.546(1) degrees, gamma = 73.499(1) degrees, V = 3043.8(7) Å(3), T = -80 degrees C, Z = 2, and R = 0.085 and R(w) = 0.095 for 5644 independent reflections with I > 3sigma(I)). The two nitrosyl units are equivalent with an average Fe-N-O angle of 167.4 +/- 0.8 degrees. Spectroscopic characterization of solid 1b revealed an NO stretch at 1785 cm(-)(1) in the infrared and Mössbauer parameters of delta = 0.67 mm s(-)(1) and DeltaE(Q) = 1.44 mm s(-)(1) at 4.2 K. These data are comparable to those for other {FeNO}(7) systems. An S = (3)/(2) spin state was assigned from magnetic susceptibility studies to the two individual {FeNO} centers, each of which has a nitrosyl ligand antiferromagnetically coupled to iron. A least-squares fit of the chi vs temperature plots to a theoretical model yielded an exchange coupling constant J of -23 cm(-)(1), where H = -2JS(1).S(2), indicating that the two S = (3)/(2) centers are antiferromagnetically coupled to one another. An extended Hückel calculation on a model complex, [Fe(2)(NO)(2)(NH(3))(6)(O(2)CH)(OH)](2+), revealed that the magnitudes of Fe-N-O angles are dictated by pi-bonding interactions between the Fe d(xz)() and NO pi orbitals.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

A Carboxylate-Bridged Non-Heme Diiron Dinitrosyl Complex

1996

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“…We present below an experiment illustrating some diverse principles of metal cluster chemistry and employing the comparatively cheap metal cobalt. Some iron cluster chemistry experiments have been reported previously in this Journal (10,11). The tricobalt cluster complexes prepared in this experiment are distinguished by their air stability, both in solution and in the solid state, that makes them ideal synthetic targets for students acquiring confidence and skill in inert atmosphere techniques.…”

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confidence: 85%