Synthesis and Application of Amino‐1<i>H</i>‐1,2,3‐triazolium Salts

Kase, Daiya; Takada, Tsuyoshi; Tsuji, Nanami; Mitsuhashi, Takuya; Haraguchi, Ryosuke

doi:10.1002/ajoc.202300108

Cited by 5 publications

References 43 publications

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Amido‐Triazole Complexes, “Normal” Triazole‐Based Imines and Metallo‐Mesoionic Imines

Rudolf,

Sarkar

2024

ChemistryEurope

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Mesoionic compounds are hugely popular in fields such as organic chemistry, organometallic chemistry and homogeneous catalysis. A new sub‐class are the mesoionic imines (MIIs). We present here 5‐amino‐4‐pyridyl‐1,2,3‐triazole as a new and versatile synthon for generating first examples of metallo‐MIIs. In this approach, we make use of metallation at the N‐pyridyl/N3‐triazole chelating pocket (instead of quarternisation of N3‐triazole) and subsequent deprotonation to generate highly versatile and tunable metallo‐MIIs. These unprecedented metallo‐MIIs contain a highly nucleophilic N‐donor site, and a tunable electrophilic metal site. Apart from displaying strong and directed H‐bonding interactions like their “classical” MII analogues, the metallo‐MIIs engage in aromatic C−F activation as well as meta−C−H activation reactions. Facile synthesis of homo and heterodincuelar complexes which contain a mixed coordinative saturation/unsaturation with these metallo‐MIIs is presented. Apart from the metallo‐MIIs we have also used 5‐amino‐4‐pyridyl‐1,2,3‐triazole as a precursor to generate the first examples of amido‐1,2,3‐triazole complexes and the first example of a “normal” (and not mesoionic) 1,2,3‐triazole based imine. Our results establish metallo‐MIIs as a versatile new class of mesoionic compounds that combine the modularity of click reactions, with the functionality of metal fragments to generate electronically ambivalent compounds with a huge potential in synthetic chemistry, catalysis and beyond.

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Amido‐Triazole Complexes, “Normal” Triazole‐Based Imines and Metallo‐Mesoionic Imines

Rudolf,

Sarkar

2024

ChemistryEurope

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Redox‐Active Triazole‐Derived Mesoionic Imines with Ferrocenyl Substituents and their Metal Complexes: Directed Hydrogen‐Bonding, Unusual C−H Activation and Ion‐Pair Formation

Rudolf,

Batman,

Mehner

et al. 2024

Chemistry A European J

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We present herein the synthesis, characterization and complexation of ferrocenyl‐substituted MIIs (mesoionic imines) and their metal complexes. In the free MIIs, strong hydrogen bonding interactions are observed between the imine‐N and the C‐H bonds of the ferrocenyl substituents both in the solid state and in solution. The influence of this hydrogen bonding is so strong that complexation of the MIIs with [IrCp*Cl2]2 yields unique six‐membered iridacycles via C‐H‐activation of the corresponding C‐H‐site at the Fc‐substituent and not the Ph‐substituent. This result is in contrast to previous reports in which always a preferential C‐H activation at the phenyl substituent is observed in competitive reactions in the presence of ferrocenyl substituents. The corresponding Ir complexes formed after in‐situ halide exchange reaction exist in either [Ir‐I] contact or as [Ir]+I‐ solvent separated ion‐pairs depending on the solvent polarity. The iodide coordinated and solvent separated ion‐pairs display drastically different physical properties. The TEP (Tolman‐electronic‐parameter) of these ligands was determined and lines up with previously reported MII‐ligands. The redox properties were investigated by a combination of electrochemical and spectroelectrochemical methods. We show here how non‐covalent interactions can have a drastic influence on the physical and chemical properties of these new class of compounds.

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Stable, aromatic, and electrophilic azepinium ions: Design using quantum chemical methods

Patra,

Gupta,

Bharatam

2024

J Comput Chem

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Cyclic nitrenium ions containing five‐membered and six‐membered rings are available, however, the seven‐membered cyclic nitrenium ions (azepinium ions) are rare. The chemistry of these species is related to their stability originating from the aromaticity due to 6π electrons. Very few theoretical and experimental studies have been conducted on the azepinium ions. Related clozapine and olanzapine cations (diazepinium ions) were observed during drug metabolism studies. In this work, quantum chemical analysis has been carried out to estimate the stability, aromaticity, and electrophilicity of several derivatives of azepinium ions. A few of the designed azepinium ions carry ΔES‐T values in the range of 50 kcal/mol favoring singlet state; π donating groups at the 2nd position increase the singlet‐triplet energy differences. Most of the substituents reduce the NICS(1) values compared to the parent system. Ring fusion with heterocyclic five‐membered rings generally increases the aromaticity and the stability of the azepinium ion ring systems. The electrophilicity parameters estimated in terms of HIA, FIA, and ω values indicate that it is possible to fine‐tune the chemical properties of azepinium ions with appropriate modulation.

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Synthesis and Application of Amino‐1H‐1,2,3‐triazolium Salts

Cited by 5 publications

References 43 publications

Amido‐Triazole Complexes, “Normal” Triazole‐Based Imines and Metallo‐Mesoionic Imines

Amido‐Triazole Complexes, “Normal” Triazole‐Based Imines and Metallo‐Mesoionic Imines

Redox‐Active Triazole‐Derived Mesoionic Imines with Ferrocenyl Substituents and their Metal Complexes: Directed Hydrogen‐Bonding, Unusual C−H Activation and Ion‐Pair Formation

Stable, aromatic, and electrophilic azepinium ions: Design using quantum chemical methods

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