Salts of Sterically Hindered Chalcogen‐Varied Herz Cations Including Those with [Te 3 Cl 14 ] 2– and [Te 4 Cl 18 ] 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 [SbCl 6 ] – anions. Reaction of in situ prepared N , N , Te ‐tris(trimethylsilyl)‐2‐amino‐3,5‐di‐ tert ‐butyltellurophenole with SeCl 4 , S 2 Cl 2 , and SOCl 2 resulted in elimination of Te and the formation of [ 4 ] 2 [TeCl 6 ], [ 1 ] 2 [Te 3 Cl 14 ], and [ 1 ] 2 [Te 4 Cl 18 ] 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 CHCl 3 ), [ 2 ][SbCl 6 ], [ 3 ][SbCl 6 ], [ 4 ][SbCl 6 ], [ 4 ] 2 [TeCl 6 ], [ 1 ] 2 [Te 3 Cl 14 ], [ 1 ] 2 [Te 4 Cl 18 ], and 11 were structurally defined by X‐ray diffraction. All of the [SbCl 6 ] – salts were isomorphous, and the [Te 3 Cl 14 ] 2– and [Te 4 Cl 18 ] 2– anions were previously unknown. Compound 11 has a significantly shortened intramolecular Te ··· O contact.