Donor-Acceptor Complexes of Tellurium Polycationic Clusters with Cyanogen

The reactions of cyanogen with Te-6[AsF6](4) and Te-4[AsF6](2) in SO2 solutions yield Te-6[AsF6](4)center dot 1.5C(2)N(2) (1) and Te-4[AsF6](2) center dot C2N2 (2) as red crystals in quantitative yield. The complexes 1 and 2 are also generated ill moderate yield by the reaction of Te, AsF5 and C2N2 in liquid SO2, but by-products are formed. These reactions show the ability of cyanogen to act as a donor towards tellurium polycations. In the crystal structures, discrete octahedral [AsF6](-) ions are present and linear cyanogen molecules. which coordinate the tellurium atoms of the polycations eta(2) by both nitrogen atoms. Ill the crystal structure of 1, the trigonal-prismatic Te-6(4+) clusters are bridged by cyanogen molecules to one-dimensional zip-zag chains. The crystal structure of 2 contains square-planar Te-4(2+) clusters, which are bridged by cyanogen molecules to two-dimensional sheets. The complexes 1 and 2 represent the first chalcogen polycationic cluster compounds containing it nitrogen ligation. The new compounds are unstable with respect to loss of cyanogen but stable under all atmosphere of C2N2. The Raman spectra of 1 and 2 were investigated and assigned. A serviceable and convenient way to handle air-sensitive and cold liquids by it transfer needle technique is described.