Chemistry - A European Journal
Chemistry - A European Journal
5 years ago

Preparation and Characterization of Group 13 Cyanides

Preparation and Characterization of Group 13 Cyanides
Monica Vasiliu, Piyush Deokar, Karl O. Christe, David A. Dixon, Trent H. Stein, Ralf Haiges
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 Me3SiCN in the presence of stoichiometric amounts of [PPh4]CN in acetonitrile solution. The 2,2′-bipyridine (bipy) adducts [(bipy)2Ga(CN)2][Ga(CN)4], [(bipy)In(CN)3], and [(bipy)Tl(CN)3] were obtained from the reaction of MF3 with Me3SiCN and bipy in acetonitrile. While the reaction of the metal trifluorides with Me3SiCN in acetonitrile resulted in recovery of the starting materials, the reaction of MF3 with Me3SiCN in pyridine (py) solution resulted in the formation of the pyridine adducts [(py)2Ga(CN)3], [(py)3In(CN)3], and [(py)2Tl(CN)3]. The cyano compounds were characterized by their vibrational spectra and, in most cases, by their X-ray crystal structures. The many ways of cyanide: Group 13 cyanides [(py)2Ga(CN)3], [(py)3In(CN)3], [(py)2Tl(CN)3], [(bipy)2Ga(CN)2][Ga(CN)4], [(bipy)In(CN)3], [(bipy)Tl(CN)3], [PPh4][Ga(CN)4], [PPh4]2[In(CN)5], and [PPh4]2[Tl(CN)5] were prepared in quantitative yields from the corresponding metal trifluorides through fluoride–cyanide exchange with Me3SiCN in the presence of pyridine (py), 2,2′-bipyridine (bipy), or [PPh4]CN.

Publisher URL: http://onlinelibrary.wiley.com/resolve/doi

DOI: 10.1002/chem.201700611

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