Coordination Chemistry of Polynitriles, Part XII—Serendipitous Synthesis of the Octacyanofulvalenediide Dianion and Study of Its Coordination Chemistry with K+ and Ag+

Abstract

The reaction of diazotetracyanocyclopentadiene with copper powder in the presence of NEt4Cl yields, unexpectedly, besides the known NEt4[C5H(CN)4] (3), the NEt4 salt of octacyanofulvalenediide (NEt4)2[C10(CN)8] (5), which can be transformed via reaction with AgNO3 to the corresponding Ag+ salt (4), which in turn can be reacted with KCl to yield the corresponding K+ salt 6. The molecular and crystal structures of 4–6 could be determined, and show a significantly twisted aromatic dianion which uses all its nitrile groups for coordination to the metals; 4 and 6 form three-dimensional coordination polymers with fourfold coordinated Ag+ and eightfold coordinated K+ cations.