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

Abstract

This 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

Quantum Chemical Interrogation of Reactions Promoted by Dirhodium Tetracarboxylate Catalysts─Mechanism, Selectivity, and Nonstatistical Dynamic Effects

“…Mechanisms of Rh 2 L 4 catalyzed reactions have been subjected to scrutiny using computational chemistry for approximately three decades, with the most attention being paid to C–H insertion reactions . In the seminal work of Taber and co-workers, molecular mechanics calculations were shown to be capable of reproducing the sense of diastereoselectivity for several Rh 2 (OAc) 4 catalyzed intramolecular C–H insertion reactions .…”

Modulating Escape Channels of Cycloheptatrienyl Rhodium Carbenes to Form Semibullvalene

“…Metal-carbene mediated chemistry has a long and winding history. 10 Our group has worked independently and collaborated closely with experimental groups to understand mechanisms of Rh-carbene mediated transformations, including C-H insertion 64,65 and ylide formation reactions, [66][67][68] with the aim of developing synthetically useful models of reactivity and selectivity. This chemistry has proven to be a playground of its own-a family of synthetically relevant organometallic reactions that display behaviors considered by some to be esoteric, but which play important roles in determining product distributions.…”

Modulating Escape Channels of Cycloheptatrienyl Rhodium Carbenes To Form Semibullvalene

“…Metal-carbene mediated chemistry has a long and winding history . Our group has worked independently and collaborated closely with experimental groups to understand mechanisms of Rh-carbene mediated transformations, including C–H insertion , and ylide formation reactions, − with the aim of developing synthetically useful models of reactivity and selectivity. This chemistry has proven to be a playground of its owna family of synthetically relevant organometallic reactions that display behaviors considered by some to be esoteric, but which play important roles in determining product distributions.…”