Department of Chemistry, Graduate School of Science, Hiroshima University, 1-3-1 Kagamiyama, Higashi-Hiroshima, 739-8526, Japan.
Department of Materials Engineering Science, Graduate School of Engineering Science, Osaka University, Toyonaka, Osaka, 560-8531, Japan.
Angew Chem Int Ed Engl. 2017 Nov 27;56(48):15234-15240. doi: 10.1002/anie.201708215. Epub 2017 Nov 2.
A triaminotriborane(3) was isolated as purple crystals through the reduction of (TMP)BCl (TMP=2,2,6,6-tetramethylpiperidino) by sodium naphthalenide. Single-crystal X-ray diffraction and computational studies of the obtained triaminotriborane(3) revealed a bent structure of the [B(NR )] chain. The bond lengths between the central and terminal boron atoms were similar to those observed in neutral diborene species. The multiple-bonding character may be best described by a three-center two-electron π-bond along the B chain. The distance between the two terminal boron atoms (2.177 Å) in the solid-state structure implies a weak interaction between them. When an excess amount of Li was used as the reducing agent, the reaction yielded an unusual dianionic species. The isolation and characterization of these two reduction products are reported herein.
通过用钠萘还原（TMP）BCl（TMP=2,2,6,6-四甲基哌啶基），得到了紫色晶体的三氨基三硼烷（3）。对获得的三氨基三硼烷（3）的单晶 X 射线衍射和计算研究表明，[B（NR）]链呈弯曲结构。中心和末端硼原子之间的键长与中性二硼烯物种中观察到的相似。多键特性可以通过 B 链上的三中心二电子π键来最好地描述。在固态结构中，两个末端硼原子之间的距离（2.177 Å）表明它们之间存在较弱的相互作用。当使用过量的 Li 作为还原剂时，反应生成了一种不寻常的二阴离子物种。本文报道了这两种还原产物的分离和表征。
