Issue 38, 2020

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

Abstract

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.

Graphical abstract: Pseudohalide HCN aggregate ions: [N3(HCN)3]−, [OCN(HCN)3]−, [SCN(HCN)2]− and [P(CN·HCN)2]−

Supplementary files

Article information

Article type
Paper
Submitted
25 Aug 2020
Accepted
11 Sep 2020
First published
15 Sep 2020

Dalton Trans., 2020,49, 13345-13351

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

J. Harloff, A. Schulz, P. Stoer and A. Villinger, Dalton Trans., 2020, 49, 13345 DOI: 10.1039/D0DT02973D

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