Synthesis and Structural Investigation of Zr(BH4)4

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• 作者：Line H. Rude ; Marta Corno ; Piero Ugliengo ; Marcello Baricco ; Young-Su Lee ; Young Whan Cho ; Flemming Besenbacher ; Jacob Overgaard ; Torben R. Jensen
• 刊名：The Journal of Physical Chemistry C
• 出版年：2012
• 出版时间：September 27, 2012
• 年：2012
• 卷：116
• 期：38
• 页码：20239-20245
• 全文大小：345K
• 年卷期：v.116,no.38(September 27, 2012)
• ISSN：1932-7455

文摘

Zirconium tetraborohydride, Zr(BH₄)₄, was synthesized by a metathesis reaction between LiBH₄ and ZrCl₄ using high-energy ball milling. Initially, a white powder was produced, and during storage at 鈭?0 掳C in a closed vial, transparent rectangular single crystals formed under the lid by vapor deposition. Single-crystal X-ray diffraction data revealed a cubic unit cell (a = 5.8387(4) 脜, space group P-43m, determined at T = 100 K), which consists of neutral Zr(BH₄)₄ molecules. The BH₄^{鈥?/sup> anions coordinate to Zr via the tetrahedral faces (畏₃). The shortest distance between neighboring molecules in the solid is defined by B鈥揌2路路路H2鈥揃 interactions of 2.77 脜. DFT calculations, based on the experimental structure, have been performed with the CRYSTAL code. A phonon instability in the 螕 point was observed for space-group symmetry P-43m, which can be eliminated by a symmetry reduction to the cubic space group P23. Computed IR spectra for the two structural models turned out to be very similar. Synthesis and decomposition was further investigated using in situ synchrotron radiation powder X-ray diffraction.}