The reaction of cyclic di(amido)- and (alkyl)(amino)-carbenes with white phosphorus in benzene afford P8 clusters supported by four carbenes, or a novel type of carbene-P4 adduct.

In the investigation of efficient chemical transformations, the carbon-carbon bond-forming reactions play an outstanding role. In this context, organocatalytic processes have achieved considerable attention.1 Beside their facile reaction course, selectivity, and environmental friendliness, new synthetic strategies are made possible. Particularly, the inversion of the classical reactivity (Umpol...

Deprotonated sydnones, which can be represented as anionic N-heterocyclic carbenes, were prepared as Li adducts and compared with deprotonated O-ethylsydnones (5-ethoxy-1,2,3-oxadiazol-4-ylidenes) which belong to the class of abnormal NHCs. The Pd complexes of the sydnone anions (X-ray analysis) as well as of the O-ethylsydnone carbenes proved to be efficient catalysts in aryl couplings of thio...

A highly efficient and stereoselective arylation of in situ-generated azavinyl carbenes affording 2,2-diaryl enamines at ambient temperatures has been developed. These transition-metal carbenes are directly produced from readily available and stable 1-sulfonyl-1,2,3-triazoles in the presence of a rhodium carboxylate catalyst. In several cases, the enamines generated in this reaction can be cycl...

LCuOTf complexes [L = cyclic (alkyl)(amino)carbenes (CAACs) or N-heterocyclic carbenes (NHCs)] selectively promote the dehydrogenative borylation of C(sp)-H bonds at room temperature. It is shown that σ,π-bis(copper) acetylide and copper hydride complexes are the key catalytic species.

Calculations were completed at the G3MP2 level on a large group of carbon- and heteroatom-substituted carbenes (X-CH, singlets and triplets), carbenium ions (X-CH2(+)), and their hydrogen addition products (X-CH3). One series includes 11 meta- and 12 para-substituted phenylcarbenes, X = Ar. Gas-phase enthalpies of reaction were calculated for four processes: singlet-triplet enthalpy gaps of the...

An (amino)(phosphino) carbene can be transformed into (amino)(phosphonio) carbenes, which undergo nucleophilic intermolecular as well as intramolecular substitution reactions at the carbene center. A variety of carbenes can be synthesized starting from a single carbene precursor. The resulting gamut of electronic and steric effects possible should open the way not only to a detailed study of th...

Contents 1. Introduction 2. Organic Chemistry a. Skeleton Structures and extensions thereof b. Molecular Orbitals and molecular interactions c. Carbenes in terms of this formalism 3. Wavefunction-based methods for computation of electronic structure a. Hartree-Fock scheme for approximating electronic structure b. Improvements on this theory c. Relationship to Organic Chemistry d. Difficulties i...

1-Sulfonyl-1,2,3-triazoles, which are readily available through copper-catalyzed azide-alkyne cycloaddition, are stable precursors to Rh–azavinyl carbenes, as well as carbene complexes of other metals. Among other transformations, these reactive intermediates can be used for the introduction of a nitrogen atom into various heterocycles that are important in both synthetic and medicinal chemistr...

Carbenes. First examples of anionic cyclic (alkyl)(amino)carbenes bearing B(CN)3 or C2F5BF2 as N-substituents are reported by Udo Radius, Maik Finze et al. in their Research Article (e202300056). Their stereo-electronic parameters were also evaluated.