Desolvation and dehydrogenation of solvated magnesium salts of dodecahydrododecaborate: Relationship between structure and thermal decomposition

Xuenian Chen*, Yi Hsin Liu, Anne Marie Alexander, Judith C. Gallucci, Son Jong Hwang, Hima Kumar Lingam, Zhenguo Huang, Cong Wang, Huizhen Li, Qianyi Zhao, Umit S. Ozkan, Sheldon G. Shore, Ji Cheng Zhao

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

13 Citations (Scopus)


Attempts to synthesize solvent-free MgB12H12 by heating various solvated forms (H2O, NH3, and CH 3OH) of the salt failed because of the competition between desolvation and dehydrogenation. This competition has been studied by thermogravimetric analysis (TGA) and temperature-programmed desorption (TPD). Products were characterized by IR, solution- and solid-state NMR spectroscopy, elemental analysis, and single-crystal or powder X-ray diffraction analysis. For hydrated salts, thermal decomposition proceeded in three stages, loss of water to form first hexahydrated then trihydrated, and finally loss of water and hydrogen to form polyhydroxylated complexes. For partially ammoniated salts, two stages of thermal decomposition were observed as ammonia and hydrogen were released with weight loss first of 14% and then 5.5%. Thermal decomposition of methanolated salts proceeded through a single step with a total weight loss of 32% with the release of methanol, methane, and hydrogen. All the gaseous products of thermal decomposition were characterized by using mass spectrometry. Residual solid materials were characterized by solid-state 11B magic-angle spinning (MAS)NMR spectroscopy and X-ray powder diffraction analysis by which the molecular structures of hexahydrated and trihydrated complexes were solved. Both hydrogen and dihydrogen bonds were observed in structures of [Mg(H2O)6B12H12]η6H 2O and [Mg(CH3OH)6B12H 12]η6CH3OH, which were determined by single-crystal X-ray diffraction analysis. The structural factors influencing thermal decomposition behavior are identified and discussed. The dependence of dehydrogenation on the formation of dihydrogen bonds may be an important consideration in the design of solid-state hydrogen storage materials.

Original languageEnglish
Pages (from-to)7325-7333
Number of pages9
JournalChemistry - A European Journal
Issue number24
Publication statusPublished - 2014 Jun 10


  • X-ray diffraction
  • boron
  • hydrogen storage
  • magnesium
  • structure elucidation

ASJC Scopus subject areas

  • General Chemistry
  • Catalysis
  • Organic Chemistry


Dive into the research topics of 'Desolvation and dehydrogenation of solvated magnesium salts of dodecahydrododecaborate: Relationship between structure and thermal decomposition'. Together they form a unique fingerprint.

Cite this