Encapsulated N‐Heterocyclic Carbenes in Silicones without Reactivity Modification

Abstract

Let them off the leash! Silicone protecting media allow the manipulation and storage of air‐ and moisture‐sensitive N‐heterocyclic carbenes (NHCs). Calculations show that a weak carbene–Lewis acid interaction minimizes decomposition of NHCs but does not inhibit NHC reactivity.

Mono‐ and Hetero‐Dinuclear Complexes of Janus‐Head NHC Ligands Possessing Backbone Phosphinoyl Groups: the Case of Soft and Hard Metal Centers

“…[30][31][32] Interestingly, such a product has recently been isolated from the reaction of 4,5-(Ph 2 P) 2 -IMe with KOH. Similar ring-opening reactions of NHCs in the presence of trace water affording formamide products have been reported by several groups.…”

N‐Heterocyclic carbenes for metal‐free polymerization catalysis: an update

“…A well‐recognized property of NHCs, namely their pronounced silicophilicity, has been exploited in polymer chemistry for the ROP of cyclic (carbo)siloxanes and the GTP of acrylates (further discussed below). In 2006, the rapid polymerization of 2,2,5,5‐tetramethyl‐1‐oxa‐2,5‐disilacyclopentane (TMOSC) was reported (Scheme , top) .…”

N-Heterocyclic carbene-catalyzed dehydration of α,ω-disilanol oligomers

“…The surprising resistance of NHCs in this system might also be explained by the weak interaction between the NHC and silicone polymers or silanol functions. In fact, we recently demonstrate the remarkable resistant character of NHCs in silicon polymers due to the weak carbene-silicon interaction (see Scheme 2) [17].…”