Pseudohalide HCN aggregate ions: [N3(HCN)3]-, [OCN(HCN)3]-, [SCN(HCN)2]- and [P(CN·HCN)2]- .,Dalton Transactions

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Pseudohalide HCN aggregate ions: [N3(HCN)3]-, [OCN(HCN)3]-, [SCN(HCN)2]- and [P(CN·HCN)2]- .
Dalton Transactions ( IF 3.5 ) Pub Date : 2020-09-15 , DOI: 10.1039/d0dt02973d
Jörg Harloff ₁ , Axel Schulz , Philip Stoer , Alexander Villinger

Affiliation

In the presence of μ-nitridobis(triphenylphosphonium) cation, [PPN]⁺, it was possible to stabilize and isolate [PPN]⁺-salts bearing the highly labile hydrogen cyanide aggregate anions of pseudohalides X (X = N₃, OCN and SCN). From a concentrated solution of the [PPN]X salts in HCN, crystals of [PPN][X(HCN)₃] (X = N₃, OCN) or [PPN][SCN(HCN)₂] could be obtained, when the crystallization was carried out fast and at low temperatures. The reaction of liquid HCN with the PCO⁻ salt led to formation of dicyanophosphide, which crystallized as HCN disolvate [P(CN·HCN)₂]⁻. All synthesized salts with hydrogen-bridged pseudohalide solvate anions are thermally unstable. Immediate loss of HCN was observed in the crystals outside the HCN solution. Oligomerization begins at ambient temperature, even in HCN solution. All discussed species were characterized by means of Raman spectroscopy, single crystal X-ray analysis and quantum-chemical calculations.

中文翻译：

伪卤化物HCN聚集离子：[N3（HCN）3]-，[OCN（HCN）3]-，[SCN（HCN）2]-和[P（CN·HCN）2]-。

在μ-氮杂双（三苯基phosph）阳离子[PPN] ⁺的存在下，可以稳定和分离带有伪卤化物X（X = N ₃，OCN和SCN的高度不稳定的氰化氢聚集阴离子）的[PPN] ^+-盐。）。从[PPN] X盐在HCN中的浓缩溶液中，可以得到[PPN] [X（HCN）₃ ]（X = N ₃，OCN）或[PPN] [SCN（HCN）₂ ]的晶体。快速且在低温下进行结晶。与PCO液体HCN的反应^-盐导致形成dicyanophosphide的，其结晶为HCN二溶剂化物[P（CN·HCN）₂ ] ^-。具有氢桥联的假卤化物溶剂化物阴离子的所有合成盐都是热不稳定的。在HCN溶液外的晶体中观察到HCN立即损失。齐聚反应在环境温度下开始，即使在HCN溶液中也是如此。所有讨论的物种都通过拉曼光谱，单晶X射线分析和量子化学计算来表征。

更新日期：2020-10-06

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