Bläsing Kevin, Harloff Jörg, Schulz Axel, Stoffers Alrik, Stoer Philip, Villinger Alexander
Anorganische Chemie, Institut für Chemie, Universität Rostock, A.-Einstein-Strasse 3a, 18059, Rostock, Germany.
Materialdesign, Leibniz-Institut für Katalyse an der Universität Rostock, A.-Einstein-Strasse 29a, 18059, Rostock, Germany.
Angew Chem Int Ed Engl. 2020 Jun 22;59(26):10508-10513. doi: 10.1002/anie.201915206. Epub 2020 Apr 21.
Although pure hydrogen cyanide can spontaneously polymerize or even explode, when initiated by small amounts of bases (e.g. CN ), the reaction of liquid HCN with [WCC]CN (WCC=weakly coordinating cation=Ph P, Ph PNPPh =PNP) was investigated. Depending on the cation, it was possible to extract salts containing the formal dihydrogen tricyanide [CN(HCN) ] and trihydrogen tetracyanide ions [CN(HCN) ] from liquid HCN when a fast crystallization was carried out at low temperatures. X-ray structure elucidation revealed hydrogen-bridged linear [CN(HCN) ] and Y-shaped [CN(HCN) ] molecular ions in the crystal. Both anions can be considered members of highly labile cyanide-HCN solvates of the type [CN(HCN) ] (n=1, 2, 3 …) as well as formal polypseudohalide ions.
尽管纯氰化氢会自发聚合甚至爆炸，但在少量碱（如CN⁻）引发下，研究了液态HCN与[WCC]CN（WCC = 弱配位阳离子 = Ph₃P、Ph₂PNPPh₂ = PNP）的反应。根据阳离子的不同，当在低温下快速结晶时，有可能从液态HCN中提取出含有形式上的二氢三氰化物[CN(HCN)₂]⁻和三氢四氰化物离子[CN(HCN)₃]⁻的盐。X射线结构解析表明，晶体中存在氢桥连的线性[CN(HCN)₂]⁻和Y形[CN(HCN)₃]⁻分子离子。这两种阴离子既可以被视为[CN(HCN)ₙ]（n = 1, 2, 3 …）类型的高度不稳定氰化物 - HCN溶剂化物的成员，也可以被视为形式上的多拟卤化物离子。
