(Benz-)imidazolin-2-ylidene-benzimidazolatonickel(II) Chelates: Syntheses, Structures, and Tuning of Noninnocent Chelate Ligand Behavior was written by Kureja, Kunal;Bruhn, Clemens;Ringenberg, Mark R.;Siemeling, Ulrich. And the article was included in Inorganic Chemistry in 2019.Application In Synthesis of 1-Methylbenzimidazole This article mentions the following:
The deprotonation of 1-(1H-benzimidazol-2-yl)-3-methylbenzimidazolium hexafluorophosphate (2MeH2[PF6]) and 1-(1H-benzimidazol-2-yl)-3-isopropylbenzimidazolium hexafluorophosphate (2iPrH2[PF6]) with potassium tert-butoxide in THF afforded the benzimidazolium-benzimidazolates 2MeH and 2iPrH. The “instant carbene” behavior of these conjugated mesomeric betaines was demonstrated by trapping their carbenic tautomers 2‘MeH and 2‘iPrH with elemental sulfur and selenium, which afforded the corresponding thio- and selenourea derivatives 2‘MeHE and 2‘iPrHE (E = S, Se). The treatment of 2MeH and 2iPrH with nickelocene furnished the nickel(II) complexes [NiCp(2‘Me)] and [NiCp(2‘iPr)], which contain an anionic C,Namido-chelating NHC ligand. The electronic structure and redox behavior of the nickel(II) chelates were investigated, as well as those of the closely related chelates [NiCp(1‘Me)] and [NiCp(1‘iPr)] derived from the corresponding imidazolium-benzimidazolates 1MeH and 1iPrH. According to DFT calculations, the HOMO is located over the NiCp moiety and the 蟺 system of the chelate ligand with a large contribution from the (benz-)imidazolate moiety. Cyclic voltammetry revealed a reversible oxidation to the monocation [NiCp(L)]+ (E1/2 = 0.315, 0.222, 0.396, 0.265 V vs. ferrocene/ferrocenium for L = 1‘Me, 1‘iPr, 2‘Me, 2‘iPr, resp.) in CH2Cl2/0.1 M n-Bu4N[B(ArF)4] (B(ArF)4– = tetrakis(3,5-bis(trifluoromethyl)phenyl)borate), and isosbestic behavior was found in UV-vis-NIR spectroelectrochem. experiments The different redox potentials reflect the different donor/acceptor properties of the NHC part of the chelate ligands, with 1′iPr being the strongest and 2‘Me the weakest net electron donor. The EPR spectroscopic signature of [NiCp(2′Me)]+ in CH2Cl2/0.1 M n-Bu4N[B(ArF)4] at 100 K is consistent with a chelate-ligand-based radical with strong spin-orbit coupling to the Ni center. In contrast, the EPR spectra of [NiCp(1‘Me)]+, [NiCp(1‘iPr)]+, and [NiCp(2‘iPr)]+ indicate that these monocations are best described as NiIII complexes, the comparatively higher contribution of the NiIII(L) vs. the NiII(L鈥?) valence tautomer being supported by the results of open-shell DFT calculations C,Namido-nickel(II) chelates [NiCp(L)] containing (benz-)imidazolin-2-ylidene-benzimidazolate ligands (L) are reversibly oxidized to [NiCp(L)]+. The [NiCp(L)] HOMO and [NiCp(L)]+ SOMO are delocalized over the NiCp unit and the (benz-)imidazolate moiety of L. The chelate ligand L can support the unusual oxidation state NiIII. Its noninnocent behavior may be tuned by the N substituent and the backbone of its NHC part, the carbene’s substitution pattern thus determining the relative contribution of the NiIII(L) vs. the NiII(L鈥?) valence tautomer of [NiCp(L)]+. In the experiment, the researchers used many compounds, for example, 1-Methylbenzimidazole (cas: 1632-83-3Application In Synthesis of 1-Methylbenzimidazole).
1-Methylbenzimidazole (cas: 1632-83-3) belongs to imidazole derivatives. Many natural products, especially alkaloids, contain the imidazole ring. These imidazoles share the 1,3-C3N2 ring but feature varied substituents. This ring system is present in important biological building blocks, such as histidine and the related hormone histamine.Application In Synthesis of 1-Methylbenzimidazole
Referemce:
Imidazole – Wikipedia,
Imidazole | C3H4N2 – PubChem