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The Lewis‐Base‐Stabilized Diphenyl‐Substituted Arsanylborane: A Versatile Building Block for Arsanylborane Oligomers
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-10-17 , DOI: 10.1002/chem.201804341 Oliver Hegen 1 , Alexander V. Virovets 1, 2, 3 , Alexey Y. Timoshkin 4 , Manfred Scheer 1
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2018-10-17 , DOI: 10.1002/chem.201804341 Oliver Hegen 1 , Alexander V. Virovets 1, 2, 3 , Alexey Y. Timoshkin 4 , Manfred Scheer 1
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The synthesis and properties of the diphenyl‐substituted arsanylborane Ph2AsBH2SMe2 (1) and Ph2AsBH2NMe3 (2) stabilized by a Lewis base (LB) were reported. These compounds were obtained by reaction of KAsPh2 with IBH2−LB (LB=SMe2, NMe3). Compounds 1 and 2 were used as starting materials for oligomeric/ polymeric arsinoboranes. The neutral species, H3B−Ph2AsBH2NMe3 (3) and Br3B−Ph2AsBH2NMe3 (4), were synthesized by reaction with H3B and Br3B, respectively. Upon reaction with IBH2−LB (LB=SMe2, NMe3), the cationic oligomeric group‐13/15‐based compounds [(Me3NBH2AsPh2BH2NMe3)]I (5) and [H2B(Ph2AsBH2NMe3)2]I (6) were obtained. All compounds were completely characterized. In addition, the oxidation of Ph2AsBH2NMe3 with chalcogens was studied. The sulfur Ph2As(S)BH2NMe3 (7 b) and selenium Ph2As(Se)BH2NMe3 (7 c) oxidation products were both isolated and fully characterized, whereas the bis(trimethylsilyl)peroxide oxidated arsinoborane Ph2As(O)BH2NMe3 (7 a) was not stable enough and could only be characterized in solution. DFT computations supported the decomposition pathway of this compound.
中文翻译：
Lewis稳定的二苯基取代的芳基硼烷：芳基硼烷低聚物的多功能构建基块
报道了由路易斯碱（LB）稳定的二苯基取代的芳基硼烷Ph 2 AsBH 2 SMe 2（1）和Ph 2 AsBH 2 NMe 3（2）的合成和性质。这些化合物通过KAsPh 2与IBH 2 -LB（LB = SMe 2，NMe 3）反应获得。化合物1和2用作低聚/聚合的砷硼烷的起始原料。中性物质H 3 B-Ph 2 AsBH 2 NMe 3（3）和Br 3 B-Ph 2 AsBH 2 NMe 3（4）分别通过与H 3 B和Br 3 B反应合成。与IBH 2 -LB（LB = SMe 2，NMe 3）反应后，阳离子低聚基团13/15基化合物[（Me 3 NBH 2 AsPh 2 BH 2 NMe 3）] I（5）和[H 2 B（Ph 2 AsBH 2 NMe 3）2 ] I（6）。所有化合物均已完全鉴定。另外，研究了硫族元素对Ph 2 AsBH 2 NMe 3的氧化作用。硫Ph 2 As（S）BH 2 NMe 3（7 b）和硒Ph 2 As（Se）BH 2 NMe 3（7 c）氧化产物均已分离并得到了充分表征，而双（三甲基甲硅烷基）过氧化物氧化了砷化硼烷Ph 2 As（O）BH 2 NMe 3（7 a）不够稳定，只能在解决方案中进行表征。DFT计算支持该化合物的分解途径。
更新日期：2018-10-17
中文翻译：
Lewis稳定的二苯基取代的芳基硼烷：芳基硼烷低聚物的多功能构建基块
报道了由路易斯碱（LB）稳定的二苯基取代的芳基硼烷Ph 2 AsBH 2 SMe 2（1）和Ph 2 AsBH 2 NMe 3（2）的合成和性质。这些化合物通过KAsPh 2与IBH 2 -LB（LB = SMe 2，NMe 3）反应获得。化合物1和2用作低聚/聚合的砷硼烷的起始原料。中性物质H 3 B-Ph 2 AsBH 2 NMe 3（3）和Br 3 B-Ph 2 AsBH 2 NMe 3（4）分别通过与H 3 B和Br 3 B反应合成。与IBH 2 -LB（LB = SMe 2，NMe 3）反应后，阳离子低聚基团13/15基化合物[（Me 3 NBH 2 AsPh 2 BH 2 NMe 3）] I（5）和[H 2 B（Ph 2 AsBH 2 NMe 3）2 ] I（6）。所有化合物均已完全鉴定。另外，研究了硫族元素对Ph 2 AsBH 2 NMe 3的氧化作用。硫Ph 2 As（S）BH 2 NMe 3（7 b）和硒Ph 2 As（Se）BH 2 NMe 3（7 c）氧化产物均已分离并得到了充分表征，而双（三甲基甲硅烷基）过氧化物氧化了砷化硼烷Ph 2 As（O）BH 2 NMe 3（7 a）不够稳定，只能在解决方案中进行表征。DFT计算支持该化合物的分解途径。
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