Preparation and Characterization of Group 13 Cyanides.

Binary Group 13 cyanides [PPh4 ][Ga(CN)4 ], [PPh4 ]2 [In(CN)5 ], and [PPh4 ]2 [Tl(CN)5 ] were obtained in quantitative yields from the corresponding metal trifluorides MF3 (M=Ga, In, Tl) by fluoride-cyanide exchange reactions with Me3 SiCN in the presence of stoichiometric amounts of [PPh4 ]CN in acetonitrile solution. The 2,2'-bipyridine (bipy) adducts [(bipy)2 Ga(CN)2 ][Ga(CN)4 ], [(bipy)In(CN)3 ], and [(bipy)Tl(CN)3 ] were obtained from the reaction of MF3 with Me3 SiCN and bipy in acetonitrile. While the reaction of the metal trifluorides with Me3 SiCN in acetonitrile resulted in recovery of the starting materials, the reaction of MF3 with Me3 SiCN in pyridine (py) solution resulted in the formation of the pyridine adducts [(py)2 Ga(CN)3 ], [(py)3 In(CN)3 ], and [(py)2 Tl(CN)3 ]. The cyano compounds were characterized by their vibrational spectra and, in most cases, by their X-ray crystal structures.