Theoretical Studies in Palladium and Platinum Molecular Chemistry

Abstract

A. Bare Metal Systems 562 B. Dinuclear Molecular Complexes 565 1. M(0)−M(0) Complexes 565 2. M(I)−M(I) Complexes 566 3. M(II)−M(II) Complexes 567 4. M(III)−M(III) and M(II)−M(IV) Complexes 570 C. Tri and Polynuclear Molecular Complexes 570 IV. Reactivity Studies 572 1. Oxidative Addition and Reductive Elimination 572 2. Migratory Insertion and Deinsertion, β-Hydride Elimination 581 3. Nucleophilic Attack on a Coordinated Ligand 587 4. Ligand Substitution Reactions 591 5. Metal-Mediated Oxidation Reactions 593 6. Studies of Catalytic Cycles 595 V. Conclusion and Perspectives 595 VI. References 596 Alain Dedieu was born in 1947 and graduated from the Ecole Nationale Supe ´rieure de Chimie de Strasbourg in 1969. He completed his Ph.D. degree from the Universite ´Louis Pasteur, Strasbourg, in 1975. After one year of postdoctoral studies with Professor Roald Hoffmann at Cornell University, he came back to the Universite ´Louis Pasteur, where he is now Directeur de Recherche at the Centre National de la Recherche Scientifique. His main research interests are in theoretical transition metal chemistry, with an emphasis on the reactivity aspects.

Phosphine–alkene ligand-mediated alkyl–alkyl and alkyl–halide elimination processes from palladium(ii)

“…In particular, establishing factors that control reductive elimination from palladium is a key objective, since it is often through this step that final product formation occurs, via either a direct (four-20 coordinate) or indirect (three-coordinate) transition state. 3,4 The rate of reductive elimination is intimately linked to the nature of the coupling partners and to the palladium's ancillary ligands, with both steric and electronic factors playing a significant contribution in each case. 5 Significant 25 effort has been devoted to studying the impact of a wide variety of ubiquitous monodentate phosphine and bidentate diphosphine metal scaffolds, with both their σ-donor character and chelate bite angle having been found to impact directly on elimination rates.…”

Computational aspects of hydroformylation

“…Transition metal computational chemistry related to homogeneous catalysis has been covered in numerous reviews. [23][24][25][26] A recent review by Tsipis provides a comprehensive summary about the applicability of DFT methods in transition metal chemistry. 27 …”

Ab initio benchmark study for the oxidative addition of CH4 to Pd: Importance of basis-set flexibility and polarization

“…2 In the group of the transition metal elements palladium is one of the most important catalysts, mostly in conjunction with ligands. 3 The insertion of the palladium atom into the C-H bond in alkanes has therefore received considerable attention, both experimentally 4 -8 and theoretically. 5,7,[9][10][11][12][13][14][15][16] In this work the insertion of the Pd-d 10 atom into the C-H bond of methane as an important example of this type of reactions has been surveyed, see Chart 1.…”