<i>In Situ</i> Observation of Elusive Dirhodium Carbenes and Studies on the Innate Role of Carboxamidate Ligands in Dirhodium Paddlewheel Complexes: A Combined Experimental and Computational Approach.

ABSTRACT: Carboxamidates as equatorial ligands in dirhodium paddlewheel catalysts are widely believed to increase selectivity at the expense of reactivity. The results of the combined experimental and computational approach described in this paper show that one has to beware of such generalizations. First, ¹⁰³Rh NMR revealed how strongly primary carboxamidates impact the electronic nature of the rhodium center they are bound to; at the same time, such ligands stabilize donor/acceptor carbenes by engaging their ester carbonyl group into peripheral interligand hydrogen bonding. This array benefits selectivity as well as reactivity if maintained along the entire reaction coordinate of a catalytic cyclopropanation. In settings where the hydrogen bond needs to be distorted for the reaction to

SUBMITTER: Peeters M 

PROVIDER: S-EPMC11440507 | biostudies-literature | 2024 Sep

REPOSITORIES: biostudies-literature