Hamdy Omar M, Pham Huong T, McArthur Scott G, Lavallo Vincent, Julian Ryan R
Department of Chemistry, University of California, Riverside, CA, 92521, USA.
Rapid Commun Mass Spectrom. 2016 May 30;30(10):1223-1227. doi: 10.1002/rcm.7547.
The icosahedral carborane anion HCB H is well known for its exceptional stability in solution and the solid state, but the gas-phase properties of this molecule have not previously been explored.
Electrospray ionization ion trap mass spectrometry, collisional activation, and isotopic labelling were used to examine the formation and reaction pathways of covalent and noncovalent carborane clusters.
Covalent attachment of an amino group to the C-vertex of HCB H dramatically alters its stability in the gas phase. Interestingly, covalently bound carborane dimers are produced during electrospray ionization. Subsequent collisional activation of these dimers leads to facile hydrogen losses (7 H molecules). The loss of H does not follow a stochastic pattern, but occurs preferentially by loss of 3 H , followed by loss of 2 H and then another 2 H molecules.
This study provides insight into new possible modes of B-H activation and functionalization in carborane cages. Copyright © 2016 John Wiley & Sons, Ltd.
二十面体碳硼烷阴离子HCBH因其在溶液和固态中具有出色的稳定性而闻名，但此前尚未对该分子的气相性质进行探索。
采用电喷雾电离离子阱质谱、碰撞活化和同位素标记来研究共价和非共价碳硼烷簇的形成及反应途径。
氨基与HCBH的C顶点共价连接极大地改变了其在气相中的稳定性。有趣的是，在电喷雾电离过程中会产生共价结合的碳硼烷二聚体。随后对这些二聚体进行碰撞活化会导致容易发生氢损失（7个H分子）。H的损失并非遵循随机模式，而是优先通过损失3个H，接着损失2个H，然后再损失2个H分子的方式发生。
本研究为碳硼烷笼中B-H活化和功能化的新可能模式提供了见解。版权所有© 2016约翰威立父子有限公司。
