Phosphines exchange in quadruply bonded metal dimers: theoretical proposal for an alternative to the internal flip mechanism

Abstract

The non-concerted jumping of two phosphine ligands from one metal center to the other in [Mo₂Cl₄(PH₃)₄] is found to be <30 kcal mol^–1 (1 cal = 4.184 J) energy costing process (DFT calculations).

References

1. F. A. Cotton and R. A. Walton, Multiple Bonds between Metal Atoms, Wiley, New York, 1982.
2. F. A. Cotton, J. L. Eglin, B. Hong and C. A. James, Inorg. Chem., 1993, 32, 2104.
3. I. F. Fraser, A. McVitie and R. D. Peacock, J. Chem. Res. (S), 1984, 420.
4. P. A. Agaskar, F. A. Cotton, D. R. Derringer, G. L. Powell, D. R. Root and T. J. Smith, Inorg. Chem., 1985, 24, 2786.
5. P. A. Agaskar and F. A. Cotton, Inorg. Chem., 1986, 25, 15.
6. F. A. Cotton and S. Kitagawa, Polyhedron, 1988, 7, 463.
7. A. McVitie and R. D. Peacock, Polyhedron, 1992, 11, 2531.
8. (a) F. A. Cotton and R. L. Luck, Inorg. Chem., 1989, 28, 4522; (b) R. G. Abbott, F. A. Cotton and L. R. Falvello, Polyhedron, 1990, 9, 1821; (c) H. Chen, F. A. Cotton and Z. Yao, Inorg. Chem., 1994, 33, 4255; (d) F. A. Cotton, E. V. Dikarev and W.-Y. Wong, Inorg. Chem., 1997, 36, 2670; (e) F. A. Cotton, E. V. Dikarev and W.-Y. Wong, Inorg. Chem., 1997, 36, 3268; (f) M. H. Chisholm, J.-H. Huang, J. C. Huffman and I. P. Parkin, Inorg. Chem., 1997, 36, 1642; (g) M. H. Chisholm, K. Folting, W. E. Streib and D.-D. Wu, Inorg. Chem., 1998, 37, 50.
9. R. H. Cayton and M. H. Chisholm, Inorg. Chem., 1991, 30, 1422.
10. C. Lee, W. Yang and R. G. Parr, Phys. Rev. B, 1988, 37, 785; A. D. Becke, J. Chem. Phys., 1993, 98, 5648; P. J. Stephens, F. J. Delvin, C. F. Chabalowski and M. J. Frisch, J. Phys. Chem., 1994, 98, 11623.
11. M. J. Frisch, G. W. Trucks, H. B. Schlegel, P. M. W. Gill, B. G. Johnson, M. A. Robb, J. R. Cheeseman, T. A. Keith, G. A. Petersson, J. A. Montgomery, K. Raghavachari, M. A. Al-Laham, V. G. Zakrzewski, J. V. Ortiz, J. B. Foresman, J. Cioslowski, B. B. Stefanov, A. Nanayakkara, M. Challacombe, C. Y. Peng, P. Y. Ayala, W. Chen, M. W. Wong, J. L. Andres, E. S. Replogle, R. Bomperts, R. L. Martin, D. J. Fox, J. S. Binkley, D. J. Defrees, J. Baker, J. J. P. Stewart, M. Head-Gordon, C. Gonzalez, J. A. Pople, Gaussian 94, Gaussian, Inc., Pittsburgh PA, 1995.
12. (a) P. J. Hay and W. R. Wadt, J. Chem. Phys., 1985, 82, 299; (b) W. R. Wadt and P. J. Hay, J. Chem. Phys., 1985, 82, 284; (c) A. Höllwarth, M. Böhme, S. Dapprich, A. W. Ehlers, A. Gobbi, V. Jonas, K. F. Köhler, R. Stegman, A. Veldkamp and G. Frenking, Chem. Phys. Lett., 1993, 208, 237; (d) W. J. Hehre, R. Ditchifeld and J. A. Pople, J. Chem. Phys., 1972, 56, 2257.
13. A. Lledos and Y. Jean, Chem. Phys. Lett., 1998, 287, 243.