An Improved Method for the Synthesis of M₂[B₁₂H₁₂] (M = Na, K) and Their Formation Mechanism

Abstract

Polyhedral boranes have potential applications in medicine and material science due to their unique structure and stability. However, tedious and low-yield synthetic methods limited their application. Herein, we have developed a facile large-scale synthetic method for M 2 [B 12 H 12 ] (M = Na, K) by the reaction of MBH 4 with N,N-dipropylaniline borane in diglyme at 120 or 140 °C in up to 88% yield. The mechanistic studies indicated that intermediates, such as [B 3 H 8 ] − and [B 9 H 14 ] − , were formed in the formation process of [B 12 H 12 ] 2− anion, similar to previously reported. The formation of B 2 H 6 from the N,N-dipropylaniline borane adducts is most important. The developed method avoided using toxic materials, with high yield, easily scaled up, raw materials are readily available. Additionally, the starting material, N,N-dipropylaniline, could be repeatedly used at least three times with similar yields, which is an economical way to facilitate industrial synthesis. It is believed that this method will support further application of Na 2 [B 12 H 12 ] and K 2 [B 12 H 12 ] as solid electrolytes for an all-solid-state batteries.