Salts of Sterically Hindered Chalcogen‐Varied Herz Cations Including Those with [Te3Cl14]2– and [Te4Cl18]2– Anions

Salts of sterically hindered chalcogen‐varied Herz cations with various anions were synthesized. 4,6‐Di‐tert‐butyl‐substituted 1,2,3‐benzothiaselenazolium (2), 2,1,3‐benzothiaselenazolium (3), and 1,2,3‐benzodiselenazolium (4) were obtained from corresponding 1,2,3‐benzodithiazolium (1) or 2‐bromo‐4,6‐di‐tert‐butylaniline (9) and were isolated as salts with [Cl]– or/and [SbCl6]– anions. Reaction of in situ prepared N,N,Te‐tris(trimethylsilyl)‐2‐amino‐3,5‐di‐tert‐butyltellurophenole with SeCl4, S2Cl2, and SOCl2 resulted in elimination of Te and the formation of [4]2[TeCl6], [1]2[Te3Cl14], and [1]2[Te4Cl18] together with N‐sulfinyl‐2‐amino‐3,5‐di‐tert‐butylphenyltellurium trichloride (11); expected 2,1,3‐benzothiatellurazolium (5) and 2,1,3‐benzoselenatellurazolium (6) were not observed. Compounds [1][Cl] (solvate with CHCl3), [2][SbCl6], [3][SbCl6], [4][SbCl6], [4]2[TeCl6], [1]2[Te3Cl14], [1]2[Te4Cl18], and 11 were structurally defined by X‐ray diffraction. All of the [SbCl6]– salts were isomorphous, and the [Te3Cl14]2– and [Te4Cl18]2– anions were previously unknown. Compound 11 has a significantly shortened intramolecular Te···O contact. Sterically hindered 1,2,3‐benzodithiazolium salts and their Se congeners with [Cl]– and [SbCl6]– anions are synthesized and structurally defined. Under identical conditions, the Te analogues unexpectedly give salts of Te‐free cations with [TeCl6]2–, [Te3Cl14]2–, and [Te4Cl18]2– anions and a neutral acyclic compound bearing TeCl3 and N=S=O groups in the ortho positions of the benzene ring.