Synthetic routes to GA(CN) 3 and MGA(CN) 4 (M = LI, CU) framework structures

Louis C. Brousseau, Darrick Williams, John Kouvetakis, M. O'Keeffe

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Abstract

Ga(CN)'3 has been prepared for the first time with a new method for preparation of inorganic cyanides. Pure crystalline material is formed by reaction of Cl 2GaN 3 with SiMe 3CN via elimination of SiMe 3N 3 and SiMe 3Cl. Reaction of GaC1 3 with SiMe 3CN also provides Ga(CN) 3. A new convenient route to GeMe 3CN and SnMe 3CN is described, but reactions of GaCl 3 with these compounds result in Lewis acid-base adducts. The composition of Ga(CN) 3 was confirmed by spectroscopic and elemental analysis. Quantitative X-ray powder diffraction was used to refine the cubic structure, which has CN groups with orientational disorder in a Prussian- blue-like network structure. The symmetry is Pm3m, a = 5.295(2) Å. Ga is octahedrally surrounded by on average three C and three N atoms with a Ga- (C,N) bond length of 2.072(2) Å, and the C-N bond length is 1,148(1) Å. LiGa(CN) 4 was prepared by reaction of Ga(CN) 3 with LiCN and was characterized by quantitative X-ray diffraction. The symmetry is P43m, a = 5.874(2) Å, and the structure consists of LiN 4 and GaC 4 tetrahedra linked by C-N bonds to form two interpenetrating networks of the Zn(CN) 2 type. CuGa(CN) 4 has a similar structure with a = 5.729(5) Å, but CuGa and/or C,N disorder cannot be ruled out.

Original languageEnglish (US)
Pages (from-to)6292-6296
Number of pages5
JournalJournal of the American Chemical Society
Volume119
Issue number27
DOIs
StatePublished - Sep 10 1997

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ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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