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Generating monovalent pnictogens within NCN pincers has resulted in the isolation of three distinct types of 1,2-azaheteroles, highly aromatic nitrogen analogues like pyrazole-based 5, aromatic yet fluxional P- and As-derived bell-clappers 1 and 2, and hypervalent Sb and Bi derivatives 3 and 4, which are supported by 3-center, 4-electron N-E-N bonds. Careful analysis of the solid-state structures of 1-5/[5-Me][OTf] in combination with NICS calculations (at the GIAO/M06/cc-pVTZ(-PP) level) and other computational methods (NBO) suggest that simpler NC chelates may support new phosphorus- and arsenic-containing heterocycles. Indeed, reduction of ECl2 (E = P or As) derivatives supported by N-Dipp (Dipp = 2,6-diisopropylphenyl) substituted NC bidentate ligands produced 1,2-benzoazaphosphole 11 and 1,2-benzoazaarsole 12. NICS calculations revealed 11 and 12 had aromatic character on par with that of pyrazole-based 5.

Complete assignments of chemical shifts in the 1H and 13C NMR spectra for a contiguous series of [(η5-C6H7)Fe(η6-MenC6H6–n)]+ and [(η5-C5H5)Fe(η6-MenC6H6–n)]+ cations (where n = 0–6) are reported. ...

The synthesis of the amino group functionalized NHC precursor 1-tert-butyl-4-(2-((dimethylamino)methyl)-phenyl)-3-phenyl-4H-1,2,4-triazol-1-ium perchlorate has been developed. The generation and bo...