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Volumn 47, Issue 16, 2008, Pages 2973-2977

Transition-metal complexes with singly reduced 1,2-diketone radical ligands

Author keywords

Density functional calculations; Iron; Ketones; Nickel; Radicals

Indexed keywords

CHEMICAL REACTIONS; LIGANDS; METAL COMPLEXES; METALLIC COMPOUNDS; TRANSITION METALS;

EID: 44949150425     PISSN: 14337851     EISSN: None     Source Type: Journal    
DOI: 10.1002/anie.200705410     Document Type: Article
Times cited : (35)

References (39)
  • 7
    • 53549085878 scopus 로고    scopus 로고
    • Crystal data for [NiIL•(cod, at 100(2) K with MoKα radiation (λ, 0.71073 Å, M r=545.42, monoclinic, space group C2/c (no. 15, a, 16.2464(5, b, 12.3107(4, c, 15.9082(5) Å, β, 112.580(3)°, Z, 4, R1, 0.0370 for 5600 reflections (I > 2σ(I, wR2, 0.1046 (all data, Crystal data for [FeIIIL•3] at 100(2) K with Mo Kα radiation (λ, 0.71073 Å, Mr, 1191.45, monoclinic, space group C2/c (no. 15, a, 10.8391(2, b, 27.8037(4, c, 23.8385(4) Å, β, 92.419(3)°, Z, 4, R1, 0.0345 for 14176 reflections (I > 2σ(I, wR2, 0.0955 all data, CCDC 668632 and 668633 contain the supplementary crystallographic data for this paper. These data can be obtained
    • r = 1191.45, monoclinic, space group C2/c (no. 15), a = 10.8391(2), b = 27.8037(4), c = 23.8385(4) Å, β = 92.419(3)°, Z = 4, R1 = 0.0345 for 14176 reflections (I > 2σ(I)), wR2 = 0.0955 (all data). CCDC 668632 and 668633 contain the supplementary crystallographic data for this paper. These data can be obtained free of charge from The Cambridge Crystallographic Data Centre via www.ccdc.cam.ac. uk/data_request/cif.
  • 8
    • 0032564853 scopus 로고    scopus 로고
    • P . Macchi, D. M. Proserpio, A Sironi, J. Am. Chem. Soc. 1998, 120, 1447.
    • P . Macchi, D. M. Proserpio, A Sironi, J. Am. Chem. Soc. 1998, 120, 1447.
  • 10
    • 53549127987 scopus 로고    scopus 로고
    • 2).
    • 2).
  • 15
    • 53549135365 scopus 로고    scopus 로고
    • This equation is derived from spin projection for a coupled system of an iron(III) ion (S, 5/2) and three aligned radicals S′, 3/2
    • This equation is derived from spin projection for a coupled system of an iron(III) ion (S = 5/2) and three aligned radicals (S′ = 3/2).
  • 23
    • 53549117357 scopus 로고    scopus 로고
    • The highest energy ligand orbital is predicted to have a very low, but non-zero, spatial overlap with the corresponding metal orbital (S = 0.01), although spin-pairing with the remaining two orbitals would force it into an antiferromagnetic alignment with respect to the Fe center. We propose, because of symmetry considerations, that this is one of three degenerate solutions.
    • The highest energy ligand orbital is predicted to have a very low, but non-zero, spatial overlap with the corresponding metal orbital (S = 0.01), although spin-pairing with the remaining two orbitals would force it into an antiferromagnetic alignment with respect to the Fe center. We propose, because of symmetry considerations, that this is one of three degenerate solutions.


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