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

  • Lando P. Wolters
  • F. Matthias BickelhauptEmail author
Chapter
Part of the Structure and Bonding book series (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.

Keywords

Activation strain model Bond activation Bond theory Catalysis Density functional calculations Halogenated phosphine ligands Ligands Transition metal complexes 

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© Springer-Verlag Berlin Heidelberg 2014

Authors and Affiliations

  1. 1.Department of Theoretical Chemistry and Amsterdam Center for Multiscale ModelingVU UniversityAmsterdamThe Netherlands
  2. 2.Institute for Molecules and MaterialsRadboud University NijmegenNijmegenThe Netherlands

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