Kinetic and Donor Stabilization of Organotellurenyl Iodides and Azides^†

The first tellurium compounds containing the extremely bulky tris(phenyldimethylsilyl)methyl (Tpsi) and 2,6-bis(2,4,6-triisopropylphenyl)phenyl (2,6-Trip2C6H3) moieties have been synthesized and isolated. Careful oxidation of the tellurolate TpsiTeLi (1) resulted in the formation of the crowded ditellane (TpsiTe)2 (2), and iodination of 2 gave the alkanetellurenyl iodide TpsiTeI (3). In a similar fashion, the terphenyl-substituted ditellane (2,6-Trip2C6H3Te)2 (9) and the arenetellurenyl iodide 2,6-Trip2C6H3TeI (10) were prepared. Reaction of the iodides TpsiTeI (3) and 2,6-Trip2C6H3TeI (10), as well as TripTeI, Mes*TeI (Trip = 2,4,6-triisopropylphenyl, Mes* = 2,4,6-tri-tert-butylphenyl), and the donor-stabilized 2-Me2NCH2C6H4TeI, with AgN3 resulted in the formation and isolation of the corresponding tellurenyl azides TpsiTeN3 (4), TripTeN3 (7), Mes*TeN3 (8), 2,6-Trip2C6H3TeN3 (11), and 2-Me2NCH2C6H4TeN3 (12). Furthermore, the corresponding tris(ethyldimethylsilyl)methyl-containing (Tesi) tellurium compounds (TesiTe)2, TesiTeI (5), and TesiTeN3 (6) have been prepared but could not be isolated in pure form. The crystal structures of TpsiTeLi (1), (TpsiTe)2 (2), TpsiTeN3 (4), 2,6-Trip2C6H3TeI (10), 2,6-Trip2C6H3TeN3 (11), and 2-Me2NCH2C6H4TeN3 (12) have been determined by X-ray diffraction. Additionally, computational studies of the molecules for which experimental structural data were available were performed.本研究合成并分离了首例含超大位阻三(苯基二甲基硅基)甲基（tris(phenyldimethylsilyl)methyl，缩写Tpsi）与2,6-双(2,4,6-三异丙基苯基)苯基（2,6-bis(2,4,6-triisopropylphenyl)phenyl，缩写为2,6-Trip2C6H3）基团的碲化合物。对碲醇盐TpsiTeLi（1）进行可控氧化，得到位阻拥挤的二碲烷(TpsiTe)2（2）；将2进行碘化反应，可制备烷基碲烯基碘化物TpsiTeI（3）。采用相似合成策略，成功得到三联苯取代的二碲烷(2,6-Trip2C6H3Te)2（9）与芳基碲烯基碘化物2,6-Trip2C6H3TeI（10）。将碘化物TpsiTeI（3）、2,6-Trip2C6H3TeI（10），以及TripTeI、Mes*TeI（其中Trip指代2,4,6-三异丙基苯基，Mes*指代2,4,6-三叔丁基苯基）与给体稳定化的2-Me2NCH2C6H4TeI，与叠氮化银（AgN3）发生反应，成功得到并分离得到对应的碲烯基叠氮化物：TpsiTeN3（4）、TripTeN3（7）、Mes*TeN3（8）、2,6-Trip2C6H3TeN3（11）以及2-Me2NCH2C6H4TeN3（12）。此外，本研究还制备了含三(乙基二甲基硅基)甲基（tris(ethyldimethylsilyl)methyl，缩写Tesi）的碲化合物：(TesiTe)2、TesiTeI（5）与TesiTeN3（6），但未能分离得到纯品。通过X射线衍射（X-ray diffraction）测定了TpsiTeLi（1）、(TpsiTe)2（2）、TpsiTeN3（4）、2,6-Trip2C6H3TeI（10）、2,6-Trip2C6H3TeN3（11）以及2-Me2NCH2C6H4TeN3（12）的晶体结构。此外，针对已获取实验结构数据的分子开展了计算研究。