Electronic Tuning of a Carbene Center via Remote Chemical Induction, and Relevant Effects in Catalysis

Abstract The present report develops the idea that an N‐heterocyclic carbene incorporating a remote anionic functionality—here, a malonate group—as a backbone component of its heterocyclic framework, can be “post‐functionalized” directly from its transition‐metal complexes, upon simple addition of a variety of electrophiles interacting directly with the malonate group in the outer coordination sphere. From a palette of selected electrophilic reagents, it was thus possible to modulate the electronic donor properties of the carbene center over a rather broad range. Both the zwitterionic complex [Rh{ malo‐ NHC}(cod)] and the cationic derivatives [Rh{ malo ‐NHC E }(cod)] + (where “ malo ‐NHC E ” represents the ligand modified by a selected electrophile “E”) were used as pre‐catalysts in two types of catalytic reactions, namely, the polymerization of phenylacetylene and the hydroboration of styrene. The results indicate that, in both cases, the zwitterionic species is by far the best catalyst, whereas a decrease in the ligand donicity induced by the added electrophile results in a concomitant reduction of catalytic activity. Apparent deviations to such a trend in the case of the hydroboration of styrene were rationalized in terms of an interaction between the reactive catecholborane substrate and the remote functionality of the N‐heterocyclic carbene leading to an in situ modification of the nature of the active species. These observations serve as a useful basis to define the scope and limitations of the present conceptual approach in catalysis.