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A Density Functional Study on [2s + 2s] Addition Reactions in Organometallic Chemistry

  • Chapter
Theoretical Aspects of Homogeneous Catalysis

Part of the book series: Catalysis by Metal Complexes ((CMCO,volume 18))

Abstract

Density Functional (DF) calculations have been carried out on organometallic [2s + 2s] addition processes. The study includes the σ-bond metathesis reaction (I): Cp2Sc-R + H-R′ → Cp2Sc-R′ ′ H-R (R = H, CH3; R′ = H, CH3, vinyl and acetylide); the double bond metathesis reaction (II): Cl2Mo(O)CH2 + H2C = CH2 → Cl2Mo(O)CH2 + H2C = CH2; and the triple bond exchange reaction (III): Cl2MoCH + HC ≡ CH→ Cl2MoCH + HC ≡ CH. An energy profile has been traced for each of the three reaction types with characterization of the four-center transition states (I) or intermediates (II, III) involved. Information is further provided on the geometries and relative energies of all reactants and products. The organometallic [2s + 2s] addition reactions are compared to the corresponding organic processes in an analysis based on qualitative molecular orbital theory.

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  1. Department of Chemistry, University of Calgary, Calgary, Alberta, T2N 1N4, Canada

    Elzbieta Folga, Tom Woo & Tom Ziegler

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  1. Elzbieta Folga
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  2. Tom Woo
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  1. Van ’t Hoff Research Institute, University of Amsterdam, The Netherlands

    Piet W. N. M. Van Leeuwen

  2. C.L. Emerson Center, Emory University, Atlanta, USA

    Keiji Morokuma

  3. Theoretical Chemistry Group, University of Utrecht, The Netherlands

    Joop H. Van Lenthe

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Folga, E., Woo, T., Ziegler, T. (1995). A Density Functional Study on [2s + 2s] Addition Reactions in Organometallic Chemistry. In: Van Leeuwen, P.W.N.M., Morokuma, K., Van Lenthe, J.H. (eds) Theoretical Aspects of Homogeneous Catalysis. Catalysis by Metal Complexes, vol 18. Springer, Dordrecht. https://doi.org/10.1007/978-94-011-0475-3_5

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