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.
ASJC Scopus subject areas
- Colloid and Surface Chemistry