메뉴 건너뛰기




Volumn 45, Issue 6, 2006, Pages 2531-2542

Orbital interactions in Fe(II)/Co(III) heterobimetallocenes: Single versus double bridge

Author keywords

[No Author keywords available]

Indexed keywords


EID: 33645534151     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic051809l     Document Type: Article
Times cited : (14)

References (70)
  • 22
    • 33645545121 scopus 로고    scopus 로고
    • note
    • This acronym is based on the bisfulvalene nomenclature.
  • 30
    • 33645548671 scopus 로고    scopus 로고
    • note
    • See Figures S1-S3 in the Supporting Information for these spectra and a more detailed discussion of the NMR data.
  • 31
    • 33645544891 scopus 로고    scopus 로고
    • See Figure S4, as well as Table S1, in the Supporting Information
    • See Figure S4, as well as Table S1, in the Supporting Information.
  • 35
    • 33645549341 scopus 로고    scopus 로고
    • note
    • 5h symmetry (cf. Supporting Information Figures S7 and S8).
  • 36
    • 33645554106 scopus 로고    scopus 로고
    • note
    • The low-energy shift of the Co orbitals is more pronounced, the higher the metal character is. The HOMO of the cobaltocenium unit is therefore calculated to be of ligand type.
  • 38
    • 33645534534 scopus 로고    scopus 로고
    • note
    • -1).
  • 39
    • 33645541052 scopus 로고    scopus 로고
    • note
    • The orbital mixing coefficient, α, is defined as being positive; the particular phases in 1 and 2 derive from the fact that the two metallocene units are connected via the cp rings and not via a direct metal-metal interaction.
  • 40
    • 33645545654 scopus 로고    scopus 로고
    • note
    • Co orbitals are admixed with ligand (cp) orbitals as in ferrocene and cobaltocenium, respectively (i.e., we are effectively considering subunit MOs).
  • 43
    • 33645541740 scopus 로고    scopus 로고
    • note
    • The ED intensity of all of these transitions is the result of the admixture of ligand (cp) orbitals and the loss of inversion symmetry in the coupled system.
  • 44
    • 33645553895 scopus 로고    scopus 로고
    • see Supporting Information for these values
    • These values have been derived from the ratio of the coefficients of the pure Fe and Co d orbitals (see Supporting Information for these values) in the HOMO and the LUMO, assuming that these coefficients are proportional to the coefficients of the corresponding metal-ligand admixed subunit orbitals, in the sense of ref 29.
  • 48
    • 33645536735 scopus 로고    scopus 로고
    • note
    • -1 for ΔG° has been taken.
  • 51
    • 33645548774 scopus 로고    scopus 로고
    • note
    • Since in dichloromethane solution the observed transition energies in metallocenic systems often show a stronger red shift than the expected one, this value has not been taken into account for the linear regression (ref 1g and references therein).
  • 53
    • 33645546884 scopus 로고    scopus 로고
    • note
    • Only the acetonitrile data were taken into account for the known reasons.
  • 54
    • 33645544229 scopus 로고    scopus 로고
    • note
    • In dichloromethane, the bandwidths are significantly smaller.
  • 62
    • 33645553279 scopus 로고    scopus 로고
    • see ref 43
    • Since the IVCT band of the bisfulvalenediiron cation has been reported to be nearly solvent independent (see ref 43), the resulting outer-sphere reorganization energy is zero.


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.