Halogenated octahydroborate salts. New route to pentaborane(9)

The chemistry of the octahydrotriborate anion [B3H8]−

“…Upon detailed analysis of the 11 B NMR data [62,76,77], the authors confirmed the structure of mono substituted products determined in [61] based on IR spectroscopy data. The 11 B NMR spectrum of disub stituted B 3 H 6 exhibits two signals, a low field sig nal at -5.3 ppm and a high field signal at -13.4 ppm, in an integrated intensity ratio of 1 : 2.…”

“…An approach to the preparation of tetraborane(10) derivatives has been developed [59,60] (9) in a yield of about 37% [61]. The reaction mixture was found to contain also diborane and traces of B 4 H 10 .…”

“…In 1975, a method for the preparation of halogenated derivatives of the B 3 anion was mentioned for the first time [61]. 3 with HCl has been found to produce B 3 H 7 [69].…”

“…39,61,69,71,72]; like electrochemical single electron oxidation[71], they afford hydrogen and unstable B 3 H 7 :[B 3 H 8 ] -+ HCl = B 3 H 7 + H 2 + Cl -. This intermediate is immediately stabilized by reacting with a Lewis base present in the reaction mix ture to give products of replacement of the terminal hydrogen atoms in B 3 H 7 L: Cl 2 in the presence of L also produce B 3 H 7 ⋅ L[73].…”

Hydrolysis of octahydrotriborate in cold acidic methanol-water solutions. Preparation of B3H7OH2 and B3H7OH-

“…By carrying out the last reaction in ether, the addition product, the thioloborate Li[BH3SH], was obtained. 4 In contrast to thioborates, thioloborates are accessible from liquid H2S at 195 K according to the equation NR4SH + BX3 <=t NR4[BX3SH].5…”