An Ab Initio Study on the Coordination of Formaldehyde, Carbon Dioxide, Dinitrogen, and Related Molecules to Iron(0) and Nickel(0) Fragments

  • M. Rosi
  • A. Sgamellotti
  • F. Tarantelli
  • C. Floriani
Part of the NATO ASI Series book series (ASIC, volume 277)


‘Ab initio’ calculations have been performed on the model systems Fe(CO) n (PH 3)4-n (η 2 - L) L = CH 2 O, CH 2 S, CMe 2 O; n = 0, 2, 4; Fe(CO)2(PH 3)2(η 2 - OCX), Fe(CO)2(PH 3)2 (η 2 - SCX), X = O, S, NH, CH 2; Fe(PH3)4(N2), Ni(PH 3)2(L), L = N 2, N 2 CH 2, N 2 H 2; to investigate the nature and the energetics of the interaction between the metal and the unsaturated ligand. The results allow a complete description of the electronic structure of the model compounds: the bonding between the metallic fragment and the unsaturated molecule lies at the very extreme of the Chatt-Dewar-Duncanson model, being dominated by the π-back-donation. The coordinate bond of CH 2 O with an iron(0) substrate and that of N 2 with a nickel(0) fragment are described in details, paying particular attention to the role of correlation effects.


Binding Energy Coordinate Bond Configuration Interaction Effective Bonding Distortion Angle 
These keywords were added by machine and not by the authors. This process is experimental and the keywords may be updated as the learning algorithm improves.


Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.


  1. 1.
    M. Rosi, A. Sgamellotti, F. Tarantelli, and C. Floriani, Inorg. Chem. 26, 3805 (1987); 27, 69 (1988); J. Organomet. Chem. 332, 153 (1987); 348, C27 (1988); J. Chem. Soc., Dalton Trans., 249 (1988); M. Rosi, A. Sgamellotti, F. Tarantelli, C. Floriani, and M.F. Guest, J. Chem. Soc., Dalton Trans., 321 (1988); M. Rosi, A. Sgamellotti, F. Tarantelli, C. Floriani, and L.S. Cederbaum, J. Chem. Soc., Dalton Trans., in press.CrossRefGoogle Scholar
  2. 2.
    M.J.S. Dewar, Bull. Soc. Chim. Fr. 18c, 71 (1951); J. Chatt and J.A. Duncanson, J. Chem. Soc., 2939 (1953).Google Scholar
  3. 3.
    V.R. Saunders and J.H. Van Lenthe, Mol. Phys. 48, 923 (1983).CrossRefGoogle Scholar
  4. 4.
    M. Dupuis, D. Spangler, and J. Wendolowski, NRCC Software Catalog, National Resource for Computation in Chemistry, Lawrence Berkeley Laboratory, University of California, Berkeley, CA, 1980, Vol. 1, Program No. QG01 (GAMESS); M.F. Guest and J. Kendrick, GAMESS User Manual, Daresbury Technical Memorandum, Daresbury Laboratory, UK, 1985.Google Scholar
  5. 5.
    H. Berke, W. Bankhardt, G. Huttner, J.v. Seyerl, and L. Zsolnai, Chem. Ber. 114, 2754 (1981)CrossRefGoogle Scholar
  6. H. Berke, G. Huttner, G. Weiler, and L. Zsolnai, J. Organomet. Chem. 219, 353 (1981).CrossRefGoogle Scholar
  7. 6.
    T.T. Tsou, J.C. Huffman, and J.K. Kochi, Inorg. Chem. 18, 2311 (1979).CrossRefGoogle Scholar
  8. 7.
    J.M. Foster and S.F. Boys, Rev. Mod. Phys. 32, 300 (1960).CrossRefGoogle Scholar
  9. 8.
    P. Conway, S.M. Grant, and A.R. Manning, J. Chem. Soc., Dalton Trans., 1920 (1979).Google Scholar
  10. 9.
    E.R. Davidson, in ‘The World of Quantum Chemistry’, eds. R. Daudel and B. Pullman, Reidel, Dordrecht, 1974.Google Scholar
  11. 10.
    S. Sakaki, K. Kitaura, and K. Morokuma, Inorg. Chem. 21, 760 (1982).CrossRefGoogle Scholar
  12. 11.
    P.E.M. Siegbahn and M.R.A. Blomberg, Chem. Phys. 87, 189 (1984).CrossRefGoogle Scholar
  13. 12.
    C.W. Bauschlicher, jr., L.G.M. Pettersson, and P.E.M. Siegbahn, J. Chem. Phys. 87, 2129 (1987).CrossRefGoogle Scholar
  14. 13.
    P.W. Jolly, K. Jonas, C. Kruger, and Y-H. Tsay, J. organomet. Chem. 33, 109 (1971)CrossRefGoogle Scholar
  15. 13.
    M. Aresta, C.F. Nobile, and A. Sacco, Inorg. Chim. Acta 12, 167 (1975).CrossRefGoogle Scholar
  16. 14.
    C.A. Tolman, D.H. Gerlach, J.P. Jesson, and R.A. Schunn, J. Organomet. Chem. 65, C23 (1974).CrossRefGoogle Scholar

Copyright information

© Kluwer Academic Publishers 1989

Authors and Affiliations

  • M. Rosi
    • 1
  • A. Sgamellotti
    • 1
  • F. Tarantelli
    • 1
  • C. Floriani
    • 2
  1. 1.Dipartimento di ChimicaUniversità di PerugiaItaly
  2. 2.ICMA Universitè de LausanneSwitzerland

Personalised recommendations