Preparation and Characterization of Antimony and Arsenic Tricyanide and Their 2,2'-Bipyridine Adducts.

Abstract

The arsenic(III) and antimony(III) cyanides M(CN)3 (M=As, Sb) have been prepared in quantitative yields from the corresponding trifluorides through fluoride-cyanide exchange with Me3 SiCN in acetonitrile. When the reaction was carried out in the presence of one equivalent of 2,2'-bipyridine, the adducts [M(CN)3 ⋅(2,2'-bipy)] were obtained. The crystal structures of As(CN)3 , [As(CN)3 ⋅(2,2'-bipy)] and [Sb(CN)3 ⋅(2,2'-bipy)] were determined and are surprisingly different. As(CN)3 possesses a polymeric three-dimensional structure, [As(CN)3 ⋅(2,2'-bipy)] exhibits a two-dimensional sheet structure, and [Sb(CN)3 ⋅(2,2'-bipy)] has a chain structure, and none of the structures resembles those found for the corresponding arsenic and antimony triazides.