1H-1,2,3-Triazol-5-ylidenes: Readily Available Mesoionic Carbenes

Abstract

Conspectus Classical carbenes are usually described as neutral compounds featuring a divalent carbon with only six electrons in their valence shell. It was only in 1988 that our group prepared the first isolable example, in which the carbene center was stabilized by a push–pull effect, using a phosphino and a silyl substituent. In the last 30 years, a myriad of acyclic and cyclic push–pull and push–push carbenes, bearing different heteroatom substituents, have been isolated. Among them, the so-called N-heterocyclic carbenes (NHCs), which include cyclic (alkyl)­(amino)­carbenes (CAACs), are arguably the most popular. They have found a vast number of applications ranging from catalysis to material science, and even in medicine. In this Account, we focus on the synthesis, structure, electronic properties, coordination, and applications of a different class of stable cyclic carbenes, namely, 1H-1,2,3-triazol-5-ylidenes. In contrast with NHCs and CAACs, these compounds have no reasonable canonical resonance forms that can be drawn showing a carbene without additional charges. According to the IUPAC, they belong to the family of mesoionic compounds and thus they are named mesoionic carbenes (MICs). In 2010, we prepared the first stable 1,2,3-triazol-5-ylidene, via a CuAAC reaction, followed by alkylation of the resulting 1,2,3-triazole, and deprotonation. Later, we synthesized more robust N3-arylated counterparts from 1,3-diarylated-1H-1,2,3-triazolium salts. Both synthetic routes can be carried out in multigram scales, making these MICS readily available. Importantly, MICs do not dimerize which contrasts with NHCs that can give the corresponding Wanzlick-type olefin. This property leads to relaxed steric requirements for their isolation; even C-unsubstituted MICs can be stored for months in the solid state at room temperature. The practicality and easily scalable syntheses of MICs allow for the preparation of polycarbenes, such as bis­(1,2,3-triazol-5-ylidenes) (i-bitz), the analogues of the well-known 2,2′-bipyridines (bpy). MIC-transition metal complexes are excellent precatalysts for variety of chemical transformations, which include hydrohydrazination of alkynes, olefin metathesis, reductive formylation of amines with carbon dioxide and diphenylsilane, hydrogenation and dehydrogenation of N-heteroarenes in water, cycloisomerization of enynes, asymmetric Suzuki–Miyaura cross-coupling, and water oxidation (WO) reactions. Besides their catalytic applications, MIC–transition metal complexes have found applications in material sciences as exemplified by the preparation of the first iron­(III) complex that is luminescent at room temperature. The peculiar properties of mesoionic triazolylidenes, combined with their enhanced stability, position them as excellent candidates to address some current challenges such as access to high-oxidation-state 3d metal complexes, the stabilization of highly reactive main group elements, the stabilization of nanoparticles, the preparation of efficient catalysts and photosensitizers based...

A Redox‐Active Heterobimetallic N‐Heterocyclic Carbene Based on a Bis(imino)pyrazine Ligand Scaffold

“…[39] Nevertheless,the extent of delocalization in MICs is reduced compared to 2,a nd therefore a p*m olecular orbital that satisfies the symmetry criteria in order to accept electron density from am etal centre is too high in energy. [40] Consequently,M ICs are quite poor p-acceptors,w hereas in the case of 2,amolecular orbital of appropriate symmetry is low in energy,accounting for the good p-accepting properties (see Figure 5, LUMO + 1).…”

Comprehensive Basicity Scales for N‐Heterocyclic Carbenes in DMSO: Implications on the Stabilities of N‐Heterocyclic Carbene and CO2 Adducts

“…There is no reasonable canonicalr esonance form that can be drawn showingacarbene without additional charges, thus according to the recommendation from IUPAC, they are named as mesoionic carbenes (MICs), but also known as the abnormal or remote NHCs (aNHCs or rNHCs). [28] As shown in Figure 7, the acidities of precursors of the selected MICs are largely dictated by the number and identityo fc omprising heteroatoms in the backbones, and cover av ery broad pK a ranging from 14.6 to 38.0 ( % 23.0 pK units), which varies along with an acidity trend of pyrazolin-4-ylidenes (R series) < imidazol-5-ylidenes (T and U series) < benzopyrazolin-5-ylidenes (S series) % 1,2,3-triazol-5-ylidene( Q series) < tetrazolylidene (V series). As also can be seen from the pK a comparison, the acidities of these MIC precursors are generally much weaker than their isomers, i.e.,1 ,2,4-triazoliums and imidazoliums, presumably,a saresult of limited resonance stabilization in the former.…”

Aerobic synthesis of N-sulfonylamidines mediated by N-heterocyclic carbene copper(I) catalysts

“…This class of catalysts was expanded through the synthesis of the pyridine derivative 4, of the heteroleptic normal/ mesoionic carbene complex 5, and of the homoleptic mesoionic triazole derivative 6 ( Figure 1). This special class of ligands presents unique electronic and steric properties and lead to unusual reactivity [23][24][25][26][27][28].…”