Local Density Functional Calculations on Metathesis Reaction Precursors

  • Dennis J. Caldwell
  • Patrick K. Redington


Calculations were carried out to assess the role of Local Density Functional (LDF) programs in following the course of metathesis reactions in large molecular systems. This study was designed to provide preliminary information on: (1) the nature of weakly bound ligands in cocatalyst structures, (2) the influence of phenyl ring substitution on catalytic activity, (3) the role of AlCl3 as a cocatalyst, and (4) the influence of macroenvironment on the basic electronic structure of the reactive site. For this purpose, calculations were carried out on an MoCl4O/tetrahydrofuran (THF) complex, ring substituted derivatives of MoCl5O-phenyl, the basic metallacyclobutane ring prototype, Mo(CH2)3CH3ClO/AlCl3, and a large fluorinated molybdenum complex.

The data indicate that atomic charges and Mayer bond orders (based on the second order density matrix) show considerable promise for making quantitative correlations (QSAR) between structure and catalytic activity. The results for the THF complex and the metallacyclobutane prototype suggest that increased catalytic activity may be associated with lowered bond orders at the active metal site. It was found that the orbital populations were 80–90% d in all cases. This is in contrast to the strong bonding associated with sp3d2 hybridization. There is evidently a certain amount of delocalization, which promotes the facile bonding changes necessary for low barrier catalysis.


Bond Order Transition Metal Complex Density Functional Method Rotational Barrier Metathesis Reaction 
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. Andzelm, J. and Wimmer, E. and Salahub, D. R., 1989. The Challenge of d and f Electrons. Theory and Computation, volume 394. ACS Symposium Series, Ed. D. Salahub and M. Zerner.Google Scholar
  2. Andzelm, J. and Wimmer, E., To Be Published.Google Scholar
  3. Anslyn, Eric V. and Brusich, Mark J. and Goddard, William A., III, 1988. Organometallics, 7:98–105.CrossRefGoogle Scholar
  4. Anslyn, Eric V. and Goddard, William A., III, 1989. Organometallics, 8:1550–1558.CrossRefGoogle Scholar
  5. Cotton, F. A. and Wilkinson, G., 1988. Advanced Inorganic Chemistry. Wiley Interscience, New York, fifth edition.Google Scholar
  6. Hohenberg, H. and Kohn, W., 1964. Phys. Rev. B, 136:864.CrossRefGoogle Scholar
  7. Kohn, W. and Sham, L. J., 1965. Phys. Rev. A, 140:1133.CrossRefGoogle Scholar
  8. Lendvay, G., 1989. J. Phys. Chem., 93:4422–4429.CrossRefGoogle Scholar
  9. Mayer, I., 1986. Int. J. Quant. Chem., 29:477–483.CrossRefGoogle Scholar
  10. Mayer, I., 1987. J. Molec. Struct., 149:81–89.Google Scholar
  11. Rappe, Anthony K. and Goddard, William A., III, 1982. J. Am. Chem. Soc., 104:448–456.CrossRefGoogle Scholar
  12. Schrock, R.R. and DePue, R.T. and Feldman, J. and Schaverien, C.J. and Dewan, J.C. and Liu, A.H., 1988. J. Am. Chem. Soc., 110:1423–1435.CrossRefGoogle Scholar

Copyright information

© Springer-Verlag New York, Inc. 1991

Authors and Affiliations

  • Dennis J. Caldwell
  • Patrick K. Redington

There are no affiliations available

Personalised recommendations