Department of Chemistry, University of Pennsylvania , Philadelphia, Pennsylvania 19104-6323, United States.
Inorg Chem. 2013 Sep 16;52(18):10690-7. doi: 10.1021/ic401844m. Epub 2013 Aug 26.
Reaction of the amine boranes NH2(R)BH3, where R = H, Me, and Bz, with 1/3 equiv of sodium hexamethyldisilazane produced the five-membered, linear aminoborane anions Na(+)[BH3N(R)HBH2N(R)HBH3(-)], where R = H (1), Me (1Me), and benzyl (1Bz). Reactions of 1 and 1Me with ammonium chloride and methylammonium chloride, respectively, resulted in elimination of NaCl and H2 to produce the linear triborazanes BH3(RNHBH2)2N(R)H2, where R = H (2) and Me (2Me), with the structure of 2 crystallographically confirmed. The reactions of 1 and 1Me with pyridine-HCl produced the pyridine-capped aminoboranes H3B(RNHBH2)2(NC5H5), where R = H (3) and Me (3Me). 2 and 2Me proved to be stable up to 90 °C but produced a mixture of products when heated above 90 °C. 2 was selectively monochlorinated at the terminal boron when treated with 1 equiv of HCl and dichlorinated when reacted with a second 1 equiv of HCl.
胺硼烷 NH2(R)BH3（其中 R = H、Me 和 Bz）与 1/3 当量的六甲基二硅氮烷钠反应，生成了五元线性氨基硼阴离子 Na(+)[BH3N(R)HBH2N(R)HBH3(-)]，其中 R = H（1）、Me（1Me）和苄基（1Bz）。1 和 1Me 分别与氯化铵和甲基氯化铵反应，消除 NaCl 和 H2，生成线性三硼嗪 BH3(RNHBH2)2N(R)H2，其中 R = H（2）和 Me（2Me），其结构通过晶体学得到证实。1 和 1Me 与吡啶-HCl 反应生成了吡啶封端的氨基硼烷 H3B(RNHBH2)2(NC5H5)，其中 R = H（3）和 Me（3Me）。2 和 2Me 在 90°C 以下稳定，但在 90°C 以上加热时会产生混合物产物。当用 1 当量的 HCl 处理时，2 可以选择性地在末端硼上进行一氯化，而当与第二当量的 HCl 反应时，则进行二氯化。
