Institut für Anorganische Chemie, Universität Regensburg, 93040, Regensburg, Germany.
Nikolaev Institute of Inorganic Chemistry, Siberian Division of Russian Academy of Sciences, Acad. Lavrentyev Prosp, 3, 630090, Novosibirsk, Russia.
Chemistry. 2018 Nov 7;24(62):16521-16525. doi: 10.1002/chem.201804341. Epub 2018 Oct 17.
The synthesis and properties of the diphenyl-substituted arsanylborane Ph AsBH SMe (1) and Ph AsBH NMe (2) stabilized by a Lewis base (LB) were reported. These compounds were obtained by reaction of KAsPh with IBH -LB (LB=SMe , NMe ). Compounds 1 and 2 were used as starting materials for oligomeric/ polymeric arsinoboranes. The neutral species, H B-Ph AsBH NMe (3) and Br B-Ph AsBH NMe (4), were synthesized by reaction with H B and Br B, respectively. Upon reaction with IBH -LB (LB=SMe , NMe ), the cationic oligomeric group-13/15-based compounds [(Me NBH AsPh BH NMe )]I (5) and [H B(Ph AsBH NMe ) ]I (6) were obtained. All compounds were completely characterized. In addition, the oxidation of Ph AsBH NMe with chalcogens was studied. The sulfur Ph As(S)BH NMe (7 b) and selenium Ph As(Se)BH NMe (7 c) oxidation products were both isolated and fully characterized, whereas the bis(trimethylsilyl)peroxide oxidated arsinoborane Ph As(O)BH NMe (7 a) was not stable enough and could only be characterized in solution. DFT computations supported the decomposition pathway of this compound.
报告了由路易斯碱 (LB) 稳定的二苯基取代胂基硼烷 PhAsBHSM e (1) 和 PhAsBHNMe (2) 的合成和性质。这些化合物是通过 KAsPh 与 IBH-LB (LB=SMe，NMe) 反应得到的。化合物 1 和 2 被用作聚合/聚合胂硼烷的起始原料。中性物质 HB-PhAsBHNMe (3) 和 BrB-PhAsBHNMe (4) 通过分别与 HB 和 BrB 反应合成。与 IBH-LB (LB=SMe，NMe) 反应后，得到阳离子寡聚物基化合物 [(MeNBHAsPhBHNMe)]I (5) 和 [HB(PhAsBHNMe)]I (6)。所有化合物都进行了完全表征。此外，还研究了 PhAsBHNMe 与硫属元素的氧化反应。分离并充分表征了硫代 PhAs(S)BHNMe (7b) 和硒代 PhAs(Se)BHNMe (7c) 氧化产物，而双(三甲基硅基)过氧化物氧化的胂硼烷 PhAs(O)BHNMe (7a) 不够稳定，只能在溶液中进行表征。DFT 计算支持了该化合物的分解途径。
