Theoretica chimica acta

, Volume 71, Issue 6, pp 411–423 | Cite as

A CASSCF and CCI study of the formation of the Ni2(C2H4) complex

  • Per-Olof Widmark
  • Björn O. Roos
Article

Abstract

Complete active space SCF and contracted CI calculations have been performed on the potential surface of the Ni2-C2H4 complex in the singlet state. The ethene geometry and position relative to Ni2 was optimized while the Ni-Ni distance was kept fixed at 2.5 Å.

Four possible symmetric geometric arrangements were considered, yielding only an end on π-bonded structure as bound. This is a consequence of the charge buildup between the nickel atoms and charge depletion at the ends, coupled with electron mobility along the bond axis, in the nickel dimer.

The energy minimum corresponds to a C2H4 moiety distorted 21% towards a C2H6 geometry, with a bond energy o 24.6 kcal/mol at the CCI level and 28.1 kcal/mol with cluster corrections included. The binding is described by a donation backdonation mechanism. These results are discussed in connection with earlier work on Ni(C2H4) and Ni2(C2H4) and in connection with experimental work.

Key words

Organometallic bonding Ni-ethene complex Bond strength Structure CASSCF-CI 

Preview

Unable to display preview. Download preview PDF.

Unable to display preview. Download preview PDF.

References

  1. 1.
    Heck RF (1974) Organotransition metal chemistry, a mechanistic approach. Academic Press, New York, p 84; Mango FD (1975) Coord Chem Rev 15:109; Khan MMT, Martell AE (1974) Homogeneous catalysis by metal complexes, vol 2. Academic Press, New York, p 77; Jolly PW, Wilke G (1974) The organic chemistry of nickel, vol 1 (organonickel compounds) Academic Press, New YorkGoogle Scholar
  2. 2.
    Ozin GA (1979) Coord Chem Rev 28:117Google Scholar
  3. 3.
    Geusic ME, Morse MD, Smalley RE (1985) J Chem Phys. 82:590Google Scholar
  4. 4.
    Ozin GA, Power WJ, Upton TH, Goddard III WA (1978) J Am Chem Soc 100:4750; Upton TH, Goddard III WA (1978) J Am Chem Soc 100:321Google Scholar
  5. 5.
    Basch H, Newton MD (1977) J Chem Phys 69:584Google Scholar
  6. 6.
    Rives AB, Fenske RF (1981) J Chem Phys 75:1293Google Scholar
  7. 7.
    Blomberg MRA, Brandemark UB, Siegbahn PEM, Broch-Mathisen K, Karlström G (1985) J Chem Phys 89:2171Google Scholar
  8. 8.
    Bauschlicher Jr CW, Bagus PS, Nelin CJ, Roos BO (1986) J Chem Phys 85:354Google Scholar
  9. 9.
    Widmark P-O, Roos BO, Siegbahn PEM (1985) J Phys Chem 89:2180Google Scholar
  10. 10.
    Widmark P-O, Sexton GJ, Roos BO (1986) Theochem 135:235Google Scholar
  11. 11.
    Blomberg MRA, Siegbahn PEM (1983) J Chem Phys 78:986; J Chem Phys (1983) 78:5682Google Scholar
  12. 12.
    Siegbahn PEM, Blomberg MRA, Bauschlicher Jr CW (1984) J Chem Phys 81:2103Google Scholar
  13. 13.
    Rösch N, Rhodin TN (1974) Faraday Discuss Chem Soc 58:28Google Scholar
  14. 14.
    Tatewaki H, Huzinaga S (1979) J Chem Phys 71:4339Google Scholar
  15. 15.
    Roos BO, Veillard A, Vinot G (1971) Theor Chim Acta 20:1Google Scholar
  16. 16.
    Huzinaga S (1984) Gaussian basis sets for molecular calculations. Elsevier, AmsterdamGoogle Scholar
  17. 17.
    Tatewaki H, Huzinaga S (1980) J Comput Chem 1:205Google Scholar
  18. 18.
    Huzinaga S (1965) J Chem Phys 42:1293Google Scholar
  19. 19.
    Roos, BO, Taylor PR, Siegbahn PEM (1980) Chem Phys 48:157; Roos BO (1980) Int J Quantum Chem S14:175; Siegbahn PEM, Almlöf J, Heiberg A, Roos BO (1981) J Chem Phys 74:2384Google Scholar
  20. 20.
    Noell JO, Newton MD, Hay. PJ, Martin RL, Bobrowitcz FW (1980) J Chem Phys 73:2360Google Scholar
  21. 21.
    Nelin CJ, Roos BO, unpublished resultsGoogle Scholar
  22. 22.
    Siegbahn PEM (1981) In: Carbo R (ed) Current aspects of quantum chemistry. Proceedings of the International Congress, Barcelona, Spain, 1981. Elsevier, Amsterdam, 1981Google Scholar
  23. 23.
    Kant A (1964) J Chem Phys 41:1872Google Scholar
  24. 24.
    Bauschlicher Jr CW, Walch SP, Langhoff SR, J Chem Phys, in pressGoogle Scholar
  25. 25.
    Hertzberg G (1966) Molecular spectra and molecular structure. III. Electronic spectra and electronic structure of polyatomic molecules. Van Nostrand, New YorkGoogle Scholar

Copyright information

© Springer-Verlag 1987

Authors and Affiliations

  • Per-Olof Widmark
    • 1
  • Björn O. Roos
    • 1
  1. 1.Department of Theoretical ChemistryChemical CentreLundSweden

Personalised recommendations