Synthesis, structure, and electronic features of (.mu.-sulfido)bis[(N,N'-ethylenebis(salicylaldiminato))iron(III)], [Fe(salen)]2S, containing the only authenticated example of the iron(III)-sulfur-iron(III) single bridge

Dorfman, Jay R.; Girerd, J.‐J.; Simhon, E. D.; Stack, T. Daniel P.; Holm, R. H.

doi:10.1021/ic00194a002

Cited by 50 publications

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“…In particular, Fe(III)-N bonds trans to the bridging oxygen are noticeably long (average 2.287(3) Å). The Fe(III)-O distance (average 1.815(3) Å) and the Fe-O-Fe angle (169.34(17)°) are both within the range of simple µ-oxodiiron(III) complexes 20. …”

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confidence: 84%

Reaction of (μ-Oxo)diiron(III) Core with CO₂ in N-Methylimidazole: Formation of Mono(μ-carboxylato)(μ-oxo)diiron(III) Complexes with N-Methylimidazole as Ligands

2003

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Several iron(III) complexes with N-methylimidazole (N-MeIm) as the ligand have been synthesized by using N-MeIm as the solvent. Under anaerobic conditions, [Fe(N-MeIm)(6)](ClO(4))(3) (1) reacts with stoichiometric amounts of water in N-MeIm to afford the (mu-oxo)diiron(III) complex, [Fe(2)(mu-O)(N-MeIm)(10)](ClO(4))(4) (3). Exposure of a solution of 3 in N-MeIm to stoichiometric and excess CO(2) gives rise to the (mu-oxo)(mu-carboxylato)diiron(III) species [Fe(2)(mu-O)(mu-HCO(2))(N-MeIm)(8)](ClO(4))(3) (4) and the methyl carbonate complex [Fe(2)(mu-O)(mu-CH(3)OCO(2))(N-MeIm)(8)](ClO(4))(3) (5), respectively. Formation of the formato-bridged complex 4 upon fixation of CO(2) by 3 in N-MeIm is unprecedentated. Methyl transfer from N-MeIm to a bicarbonato-bridged (mu-oxo)diiron(III) intermediate appears to give rise to 5. Complex 3 is a good starting material for the synthesis of (mu-oxo)mono(mu-carboxylato)diiron(III) species [Fe(2)(mu-O)(mu-RCO(2))(N-MeIm)(8)](ClO(4))(3) (where R = H (4), CH(3) (6), or C(6)H(5) (7)); addition of the respective carboxylate ligand in stoichiometric amount to a solution of 3 in N-MeIm affords these complexes in high yields. Attempts to add a third bridge to complexes 4, 6, and 7 to form the (mu-oxo)bis(mu-carboxylato)diiron(III) species result in the isolation of the previously known triiron(III) mu-eta(3)-oxo clusters [[Fe(mu-RCO(2))(2)(N-MeIm)](3)O](ClO(4)) (8). The structures of 3, 4, 6, and 7 allow one, for the first time, to inspect the various features of the [Fe(2)(mu-O)(mu-RCO(2))](3+) moiety with no strain from the ligand framework.

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confidence: 84%

Reaction of (μ-Oxo)diiron(III) Core with CO₂ in N-Methylimidazole: Formation of Mono(μ-carboxylato)(μ-oxo)diiron(III) Complexes with N-Methylimidazole as Ligands

2003

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“…amine)] and their X-ray studies have widely been presented in the literature[5][6][7][8][9]. Kessel and Hendrickson[10] have studied Schiff base complexes of iron(III) incorporating p-quinone bridges.…”

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confidence: 99%

Complexes of iron(III) salen and saloph Schiff bases with bridging 2,4,6-tris(2,5-dicarboxyphenylimino-4-formylphenoxy)-1,3,5-triazine and 2,4,6-tris(4-carboxyphenylimino-4′-formylphenoxy)-1,3,5-triazine

Koç

Uçan

2007

Transition Met Chem

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Complexes of iron(III) salen and saloph Schiff bases with bridging 2,4,6-tris(2,5-dicarboxyphenylimino-4-formylphenoxy)-1,3,5-triazine and 2,4,6-tris(4-carboxyphenylimino-4¢-formylphenoxy)-1,3,5-triazine Abstract Four new trinuclear Fe(III) complexes involving tetradenta Schiff bases N,N 1 -bis(salicylidene) ethylenediamine-(salenH 2 ) or bis(salicylidene)-o-phenylenediamine-(salophH 2 ) with 2,4,6-tris(2,5-dicarboxyphenylimino-4-formylphenoxy)-1,3,5-triazine (DCPI-TRIPOD) or 2,4,6-tris(4-carboxyphenylimino-4¢-formylphenoxy)-1,3,5-triazine (CPI-TRIPOD) have been synthesized and characterized by means of elemental analysis carrying out 1 H-n.m.r., i.r. spectroscopy, thermal analyses and magnetic susceptibility measurements. The complexes can also be characterized as high-spin distorted octahedral Fe III bridged by carboxylic acids. The tricarboxylic acids play a role as bridges for weak antiferromagnetic intramolecular exchange.

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“…A paramount dependence of the magnetic exchange interactions would be in agreement with similar observations made for related binuclear transition metal thiophenolate complexes. [32,52,53] Moreover, the different structure of the ligands in the Ni3-and Ni2-complexes causes opposite signs of the magnetic anisotropy. Thus, in the Ni3-complex the ligand structure yields the positive axial anisotropy and, therefore, an easy plane situation for the molecule.…”

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confidence: 99%

Interplay of Magnetic Exchange Interactions and NiSNi Bond Angles in Polynuclear Nickel(II) Complexes

Krupskaya¹,

Alfonsov²,

Parameswaran³

et al. 2010

ChemPhysChem

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The ability of bridging thiophenolate groups (RS -) to transmit magnetic exchange interactions between paramagnetic Ni(II) ions has been examined. Specific attention was paid to complexes with large Ni-SR-Ni angles. For this purpose, dinuclear [Ni2Land trinuclear [Ni3L 2 (OAc)2][BPh4]2 (3), where H2L 1 and H2L 2 represent 24-membered macrocyclic amino-thiophenol ligands, were prepared and fully characterized by IR-and UV-vis spectroscopy, X-ray crystallography, static magnetization M measurements and high-field electron spin resonance (HF-ESR). The dinuclear complex 2 has a central N3Ni2(-S)2(-OAc)Ni2N3 core with a mean Ni-S-Ni angle of 92°. The macrocycle L 2 supports a trinuclear complex 3, with distorted octahedral N2O2S2 and N2O3S coordination environments for one central and two terminal Ni(II) ions, respectively. The Ni-S-Ni angles are at 132.8° and 133.5°. We find that the variation of the bond angles has a very strong impact on the magnetic properties of the Ni complexes. In the case of the Ni2-complex, temperature T and magnetic field B dependencies of M reveal a ferromagnetic coupling J = -29 cm -1 between two Ni(II) ions (H = JS1S2). HF-ESR measurements yield a negative axial magnetic anisotropy (D < 0) which implies a bistable (easy axis) magnetic ground state. In contrast, for the Ni3-complex we find an appreciable antiferromagnetic coupling J' = 97 cm -1 between the Ni(II) ions and a positive axial magnetic anisotropy (D > 0) which implies an easy plane situation.

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Synthesis, structure, and electronic features of (.mu.-sulfido)bis[(N,N'-ethylenebis(salicylaldiminato))iron(III)], [Fe(salen)]2S, containing the only authenticated example of the iron(III)-sulfur-iron(III) single bridge

Cited by 50 publications

References 0 publications

Reaction of (μ-Oxo)diiron(III) Core with CO₂ in N-Methylimidazole: Formation of Mono(μ-carboxylato)(μ-oxo)diiron(III) Complexes with N-Methylimidazole as Ligands

Reaction of (μ-Oxo)diiron(III) Core with CO₂ in N-Methylimidazole: Formation of Mono(μ-carboxylato)(μ-oxo)diiron(III) Complexes with N-Methylimidazole as Ligands

Complexes of iron(III) salen and saloph Schiff bases with bridging 2,4,6-tris(2,5-dicarboxyphenylimino-4-formylphenoxy)-1,3,5-triazine and 2,4,6-tris(4-carboxyphenylimino-4′-formylphenoxy)-1,3,5-triazine

Interplay of Magnetic Exchange Interactions and NiSNi Bond Angles in Polynuclear Nickel(II) Complexes

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Synthesis, structure, and electronic features of (.mu.-sulfido)bis[(N,N'-ethylenebis(salicylaldiminato))iron(III)], [Fe(salen)]2S, containing the only authenticated example of the iron(III)-sulfur-iron(III) single bridge

Cited by 50 publications

References 0 publications

Reaction of (μ-Oxo)diiron(III) Core with CO2 in N-Methylimidazole: Formation of Mono(μ-carboxylato)(μ-oxo)diiron(III) Complexes with N-Methylimidazole as Ligands

Reaction of (μ-Oxo)diiron(III) Core with CO2 in N-Methylimidazole: Formation of Mono(μ-carboxylato)(μ-oxo)diiron(III) Complexes with N-Methylimidazole as Ligands

Complexes of iron(III) salen and saloph Schiff bases with bridging 2,4,6-tris(2,5-dicarboxyphenylimino-4-formylphenoxy)-1,3,5-triazine and 2,4,6-tris(4-carboxyphenylimino-4′-formylphenoxy)-1,3,5-triazine

Interplay of Magnetic Exchange Interactions and NiSNi Bond Angles in Polynuclear Nickel(II) Complexes

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Reaction of (μ-Oxo)diiron(III) Core with CO₂ in N-Methylimidazole: Formation of Mono(μ-carboxylato)(μ-oxo)diiron(III) Complexes with N-Methylimidazole as Ligands

Reaction of (μ-Oxo)diiron(III) Core with CO₂ in N-Methylimidazole: Formation of Mono(μ-carboxylato)(μ-oxo)diiron(III) Complexes with N-Methylimidazole as Ligands