Pd-NHC (PEPPSI) complexes: Synthetic utility and computational studies into their reactivity

This review concentrates on the results obtained thus far in cross-coupling reactions utilising Pd-PEPPSI-IPr (pre)catalyst. Results from computational studies expose possible factors behind the high reactivity of this complex, as well as mechanistic details for the IPr-Pd-mediated alkyl-alkyl Negishi cross-coupling. 1 Introduction 2 Evolution to Pd-PEPPSI Complexes 2.1 Background of NHCs; Unraveling Electronic and Steric Components 2.2 Design and Preparation of Pd-PEPPSI Complexes 2.3 Mechanism of Activation and Role in the Catalytic Cycle 3 Cross-Coupling Results with Pd-PEPPSI Complexes 3.1 General Cross-Coupling Scheme 3.2 The Suzuki-Miyaura Reaction 3.3 The Kumada-Tamao-Corriu Reaction 3.4 The Negishi Reaction 3.5 Buchwald-Hartwig-Yagupol'skii Amination 4 Theory and Computation 4.1 Theory 4.2 Computation 4.3 Geometric Structure 4.4 Reaction Profile 4.5 Interactions 4.6 Atoms-in-Molecules 5 Conclusions.