Transient carbenes are among the most important and versatile reactive intermediates in chemistry, and therefore play key roles in a large number of reactions. In protic solvents, such as water or alcohols, carbenes can be extremely short-lived with lifetimes in the order of picoseconds. In our group, we use Quantum Mechanics (QM) and multiscale approaches (QM/MM) to investigate the reactivity and dynamics of transient carbenes in organic solvents (Figure) and cryogenic matrices.<br/>Among others, we investigated the reactions of the archetypal arylcarbenes diphenylcarbene (DPC) and fluorenylidene with protic solvents to identify the possible reaction mechanisms. For DPC, the solvent mixing ratio allows us to control the reaction channels and the lifetime of the intermediate cation. A similar effect to that of protic solvents was found for halogen bond donors on DPC.<br/>On the methodological side, we recently undertook the implementation of theoretical tools for studying intersystem crossing and tunneling in carbenes. Additionally, we implemented a hybrid QM/MM/Coarse Grain (CG) multi-resolution approach, which can reduce computation times by 40-75% relative to fully atomistic DFT/MM calculations. In this way, we provide with novel tools to study the dynamic behavior of challenging reactive species like carbenes.

Dynamics simulations of reactive intermediates: From cryogenic matrices to co-solvents

256th National Meeting (2018)

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