Abstract
‘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.
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References
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.
M.J.S. Dewar, Bull. Soc. Chim. Fr. 18c, 71 (1951); J. Chatt and J.A. Duncanson, J. Chem. Soc., 2939 (1953).
V.R. Saunders and J.H. Van Lenthe, Mol. Phys. 48, 923 (1983).
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.
H. Berke, W. Bankhardt, G. Huttner, J.v. Seyerl, and L. Zsolnai, Chem. Ber. 114, 2754 (1981)
H. Berke, G. Huttner, G. Weiler, and L. Zsolnai, J. Organomet. Chem. 219, 353 (1981).
T.T. Tsou, J.C. Huffman, and J.K. Kochi, Inorg. Chem. 18, 2311 (1979).
J.M. Foster and S.F. Boys, Rev. Mod. Phys. 32, 300 (1960).
P. Conway, S.M. Grant, and A.R. Manning, J. Chem. Soc., Dalton Trans., 1920 (1979).
E.R. Davidson, in ‘The World of Quantum Chemistry’, eds. R. Daudel and B. Pullman, Reidel, Dordrecht, 1974.
S. Sakaki, K. Kitaura, and K. Morokuma, Inorg. Chem. 21, 760 (1982).
P.E.M. Siegbahn and M.R.A. Blomberg, Chem. Phys. 87, 189 (1984).
C.W. Bauschlicher, jr., L.G.M. Pettersson, and P.E.M. Siegbahn, J. Chem. Phys. 87, 2129 (1987).
P.W. Jolly, K. Jonas, C. Kruger, and Y-H. Tsay, J. organomet. Chem. 33, 109 (1971)
M. Aresta, C.F. Nobile, and A. Sacco, Inorg. Chim. Acta 12, 167 (1975).
C.A. Tolman, D.H. Gerlach, J.P. Jesson, and R.A. Schunn, J. Organomet. Chem. 65, C23 (1974).
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© 1989 Kluwer Academic Publishers
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Rosi, M., Sgamellotti, A., Tarantelli, F., Floriani, C. (1989). An Ab Initio Study on the Coordination of Formaldehyde, Carbon Dioxide, Dinitrogen, and Related Molecules to Iron(0) and Nickel(0) Fragments. In: Laganà, A. (eds) Supercomputer Algorithms for Reactivity, Dynamics and Kinetics of Small Molecules. NATO ASI Series, vol 277. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0945-8_6
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DOI: https://doi.org/10.1007/978-94-009-0945-8_6
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