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d10-ML2 Complexes: Structure, Bonding, and Catalytic Activity

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Book cover Computational Studies in Organometallic Chemistry

Part of the book series: Structure and Bonding ((STRUCTURE,volume 167))

Abstract

Our goal in this chapter is to show how one can obtain a better understanding of the decisive factors for the selectivity and efficiency of catalytically active metal complexes. This ongoing research project has been designated the ‘Fragment-oriented Design of Catalysts’ and aims at providing design principles for a more rational development of catalysts. To this end, we have performed a series of studies in which we systematically investigate the effect of a specific variation on the reactivity of the catalyst. Thus, we will summarize previous results on not only how the reaction barrier varies when different bonds are activated by palladium, different ligands are attached to palladium but also how different metal centers perform compared to palladium. In a final section, we present a case study on newly obtained results about the effect of adding substituents with different electronegativity to the phosphine ligands at the metal center. A red thread throughout the chapter, and our methodology in general, is the application of the activation strain model of chemical reactivity. This is a predictive model that provides a quantitative relationship between trends in barrier heights and variation of geometric and electronic properties of the reactants.

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Notes

  1. 1.

    We have performed a geometry optimization of Pd(PCl3)2 at the computational level described in reference 49, resulting in a P–Pd–P angle of 135.5°. We find that the linear conformer is 1.4 kcal mol−1 higher in energy, with two degenerate imaginary frequencies, both corresponding to bending the complex.

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Authors and Affiliations

  1. Department of Theoretical Chemistry and Amsterdam Center for Multiscale Modeling, VU University, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands

    Lando P. Wolters & F. Matthias Bickelhaupt

  2. Institute for Molecules and Materials, Radboud University Nijmegen, Heyendaalseweg 135, 6525 AJ, Nijmegen, The Netherlands

    F. Matthias Bickelhaupt

Authors
  1. Lando P. Wolters
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  2. F. Matthias Bickelhaupt
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Correspondence to F. Matthias Bickelhaupt .

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Editors and Affiliations

  1. Institute of Chemical Sciences, Heriot-Watt Unversity, Edinburgh, United Kingdom

    Stuart A. Macgregor

  2. Institut Charles Gerhardt; UMR 5253-CNRS-UM-ENSCM, Université de Montpellier; Place E. Bataillon, Montpellier, France

    Odile Eisenstein

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Wolters, L.P., Bickelhaupt, F.M. (2014). d10-ML2 Complexes: Structure, Bonding, and Catalytic Activity. In: Macgregor, S., Eisenstein, O. (eds) Computational Studies in Organometallic Chemistry. Structure and Bonding, vol 167. Springer, Cham. https://doi.org/10.1007/430_2014_147

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