메뉴 건너뛰기




Volumn 120, Issue 29, 1998, Pages 7239-7251

Unsupported Ti-Co and Zr-Co bonds in heterobimetallic complexes: A theoretical description of metal-metal bond polarity

Author keywords

[No Author keywords available]

Indexed keywords

COBALT DERIVATIVE; TITANIUM DERIVATIVE; ZIRCONIUM DERIVATIVE;

EID: 0032578156     PISSN: 00027863     EISSN: None     Source Type: Journal    
DOI: 10.1021/ja974160v     Document Type: Article
Times cited : (93)

References (45)
  • 23
    • 3543023524 scopus 로고    scopus 로고
    • note
    • In general, the B3LYP charges suggest a slightly more ionic character of the density. This may be interpreted as being due to the fact that the B3LYP functional contains an intermediate between a pure (gradient corrected) exchange functional and the Hartree-Fock exchange functional; the Hartree-Fock theory being known to yield somewhat too ionic electron densities.
  • 24
    • 3543037198 scopus 로고    scopus 로고
    • note
    • In CDA, the molecular orbitals of the complex are broken down into contributions from occupied and virtual orbitals of the charged closed-shell fragments.
  • 26
    • 3543035433 scopus 로고    scopus 로고
    • note
    • We would like to point out that CDA performs an analysis of the complex MOs in terms of fragment MOs and that the nonorthogonality of the MOs of different fragments may lead to similar difficulties as encountered in MPA, especially when the basis set contains diffuse functions. We have looked into this by carrying out a CDA using a small SVDP basis set described in the calculational section at the end of this paper since this basis set does not contain diffuse d functions in contrast to the TZVDP basis set employed in all our calculations. In this case, the negative back-bonding term is indeed smaller (b ≈ 0.1); however, the residual term Δ is even larger (between -0.17 and -0.23 depending on the compound and the density functional employed).
  • 28
    • 0000809379 scopus 로고
    • Based on similar observations, it was argued that AIM populations suffer from an artificial charge transfer from an atom with low electronegativity to an adjacent atom with large electronegativity, which was claimed solely to be the consequence of atomic orbital size and not due to differences in electronegativity: Perrin, C. L. J. Am. Chem. Soc. 1991, 113, 2865. It has been demonstrated, however, that the above argument relies on an oversimplified model and that AIM populations do not depend on atomic size: Gatti, C.; Fantucci, P. J. Phys. Chem. 1993, 97, 11677.
    • (1991) J. Am. Chem. Soc. , vol.113 , pp. 2865
    • Perrin, C.L.1
  • 29
    • 0037635546 scopus 로고
    • Based on similar observations, it was argued that AIM populations suffer from an artificial charge transfer from an atom with low electronegativity to an adjacent atom with large electronegativity, which was claimed solely to be the consequence of atomic orbital size and not due to differences in electronegativity: Perrin, C. L. J. Am. Chem. Soc. 1991, 113, 2865. It has been demonstrated, however, that the above argument relies on an oversimplified model and that AIM populations do not depend on atomic size: Gatti, C.; Fantucci, P. J. Phys. Chem. 1993, 97, 11677.
    • (1993) J. Phys. Chem. , vol.97 , pp. 11677
    • Gatti, C.1    Fantucci, P.2
  • 34
    • 3543047578 scopus 로고    scopus 로고
    • note
    • It should be noted that for homopolar bonds the positions of the bond critical points of AIM theory and of the ELF maxima will agree and that the ELF distribution will be symmetrical around that point.
  • 37
    • 79960364722 scopus 로고    scopus 로고
    • Center for Scientific Computing: Espoo, Finland
    • Laaksonen, L. gOpenMol; Center for Scientific Computing: Espoo, Finland, 1997.
    • (1997) gOpenMol
    • Laaksonen, L.1
  • 38
    • 3543014007 scopus 로고    scopus 로고
    • Jansen, G. Unpublished results
    • Jansen, G. Unpublished results.
  • 39
    • 0004261805 scopus 로고
    • Supercomputer Computations Research Institute, Florida State University: Tallahassee
    • Pepke, E.; Murray, J.; Lyons, J.; Hwu, T.-Z. SciAn; Supercomputer Computations Research Institute, Florida State University: Tallahassee, 1993.
    • (1993) SciAn
    • Pepke, E.1    Murray, J.2    Lyons, J.3    Hwu, T.-Z.4


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.