Melding of Experiment and Theory Illuminates Mechanisms of Metal-Catalyzed Rearrangements: Computational Approaches and Caveats

Abstract

AbstractThis review summarizes approaches and caveats in computational modeling of transition-metal-catalyzed sigmatropic rearrangements involving carbene transfer. We highlight contemporary examples of combined synthetic and theoretical investigations that showcase the synergy achievable by integrating experiment and theory.1 Introduction2 Mechanistic Models3 Theoretical Approaches and Caveats3.1 Recommended Computational Tools3.2 Choice of Functional and Basis Set3.3 Conformations and Ligand-Binding Modes3.4 Solvation4 Synergy of Experiment and Theory – Case Studies4.1 Metal-Bound or Free Ylides?4.2 Conformations and Ligand-Binding Modes of Paddlewheel Complexes4.3 No Metal, Just Light4.4 How To ‘Cope’ with Nonstatistical Dynamic Effects5 Outlook