Competitive solvent-molecule interactions govern primary processes of diphenylcarbene in solvent mixtures.

ABSTRACT: Photochemical reactions in solution often proceed via competing reaction pathways comprising intermediates that capture a solvent molecule. A disclosure of the underlying reaction mechanisms is challenging due to the rapid nature of these processes and the intricate identification of how many solvent molecules are involved. Here combining broadband femtosecond transient absorption and quantum mechanics/molecular mechanics simulations, we show for one of the most reactive species, diphenylcarbene, that the decision-maker is not the nearest solvent molecule but its neighbour. The hydrogen bonding dynamics determine which reaction channels are accessible in binary solvent mixtures at room temperature. In-depth analysis of the amount of nascent intermediates corroborates the importance of a hy

SUBMITTER: Knorr J 

PROVIDER: S-EPMC5059701 | biostudies-literature | 2016 Oct

REPOSITORIES: biostudies-literature