Here we present a protocol for the synthesis of two distinct carbonyl-decorated carbenes. Both carbenes can be prepared using nearly identical procedures in multi-gram scale quantities. The goal of this manuscript is to clearly detail how to handle and prepare these unique carbenes such that a synthetic chemist of any skill level can work with them. The two carbenes described are a diamidocarbe...

Cyclotriarsanes are rare and described herein is a scalable synthetic protocol towards aryl-substituted derivatives. Their reactivity [Cp2Ti(C2(SiMe3)2)], affording titanocene diarsene complexes, N-heterocyclic carbenes (NHCs) discussed.

1,1’-Diaminoferrocene (1) was converted to α-aminonitriles fc[NHC(CN)MeR’]2 (fc=1,1’-ferrocenediyl; 2 a: R’=Me, b: R’=Ph, c: R’=tBu) by reaction with ketones MeC(O)R’ in the presence of NaCN/HOAc or diimine fc(N=CPh2)2 (3) condensation Ph2CO. Treatment a–c 3 MeLi furnished fc(NHR)2 (4 R=tBu, 4 R=CMe2Ph, R=CMe2tBu, d: R=CMePh2) after aqueous work-up. The formylative cyclisation a–d fc[(NR)2CH][B...

The effect of substituents at the heteroatom on the electronic structures of different N-heterocyclic carbenes (1, 2 and 3), silylene (4) and germylene (5) are examined using Density Functional Theory. The kinetic and thermodynamic stabilities of these molecules are assessed by examining the HOMO-LUMO gap and hydrogenation energies, respectively. The extent of cyclic electron delocalization pre...

ABSTRACT New indenylidene-type second generation catalysts bearing modified unsymmetrically substituted N-heterocyclic carbene ligands were synthesized. The complexes contain an N-mesityl and N'-nitrobenzyl substituted NHC ligand. The precursors of free carbenes-imidazolinium salts-were obtained in an easy and environment-friendly way (under aqueous or neat conditions). The new catalysts were p...