New Series of Intramolecularly Coordinated Diaryltellurium Compounds. Rational Synthesis of the Diarylhydroxytelluronium Triflate [(8-Me₂NC₁₀H₆)₂Te(OH)](O₃SCF₃)

The reaction of 8-dimethylaminonaphthyllithium etherate with the tellurium­(II) bis­(dithiocarbamate) Te­(S2CNEt2)2 provided the diaryltelluride (8-Me2NC10H6)2Te (1). The oxidation of 1 with an excess of H2O2 did not afford the expected diaryltellurium­(IV) oxide (8-Me2NC10H6)2TeO (2), but the diaryltellurium­(VI) dioxide (8-Me2NC10H6)2TeO2 (3). The preparation of 2 was achieved by the comproportionation reaction of 1 and 3. The protonation of 2 using triflic acid gave rise to the formation of diarylhydroxytelluronium triflate [(8-Me2NC10H6)2Te­(OH)]­(O3SCF3) (4), which features the protonated diaryltellurium oxide [(8-Me2NC10H6)2Te­(OH)]+ (4a). Compounds 1, 3·H2O·H2O2, 3·2H2O, and 4 were characterized by X-ray crystallography. The experimentally obtained molecular structures were compared to those calculated for 1–3, 4a, and (8-Me2NC10H6)2Te­(OH)2 (5) as well as the related diphenyltellurium compounds Ph2Te (6), Ph2TeO (7), Ph2TeO2 (8), [Ph2Te­(OH)]+ (9a), and Ph2Te­(OH)2 (10) at the DFT/B3PW91 level of theory.醚合8-二甲氨基萘基锂（8-dimethylaminonaphthyllithium etherate）与二(二硫代氨基甲酸)碲(II)（tellurium(II) bis(dithiocarbamate)）Te(S2CNEt2)2发生反应，得到二芳基碲（diaryltelluride）(8-Me2NC10H6)2Te（化合物1）。对化合物1采用过量过氧化氢（H2O2）进行氧化，并未得到预期的二芳基氧化碲(IV)（diaryltellurium(IV) oxide）(8-Me2NC10H6)2TeO（化合物2），而是生成了二芳基二氧化碲(VI)（diaryltellurium(VI) dioxide）(8-Me2NC10H6)2TeO2（化合物3）。化合物2的制备可通过化合物1与3的归中反应（comproportionation reaction）实现。使用三氟甲磺酸（triflic acid）对化合物2进行质子化，得到二芳基羟碲鎓三氟甲磺酸盐（diarylhydroxytelluronium triflate）[(8-Me2NC10H6)2Te(OH)](O3SCF3)（化合物4），该化合物包含质子化的二芳基氧化碲阳离子[(8-Me2NC10H6)2Te(OH)]+（4a）。通过X射线晶体衍射（X-ray crystallography）对化合物1、3·H2O·H2O2、3·2H2O及4进行了结构表征。将实验测得的分子结构与1~3、4a以及二(8-二甲氨基萘基)二氢氧化碲（(8-Me2NC10H6)2Te(OH)2，化合物5）、相关二苯基碲类化合物二苯基碲（Ph2Te，化合物6）、二苯基氧化碲（Ph2TeO，化合物7）、二苯基二氧化碲（Ph2TeO2，化合物8）、[二苯基羟碲鎓]阳离子([Ph2Te(OH)]+，9a)以及二苯基二氢氧化碲（Ph2Te(OH)2，化合物10）在密度泛函理论/B3PW91（DFT/B3PW91）理论水平下的计算结果进行了对比。