Dataset Information

Salts of HCN-Cyanide Aggregates: [CN(HCN)2 ]- and [CN(HCN)3 ].

ABSTRACT: 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=Ph4 P, Ph3 PNPPh3 =PNP) was investigated. Depending on the cation, it was possible to extract salts containing the formal dihydrogen tricyanide [CN(HCN)2 ]- and trihydrogen tetracyanide ions [CN(HCN)3 ]- from liquid HCN when a fast crystallization was carried out at low temperatures. X-ray structure elucidation revealed hydrogen-bridged linear [CN(HCN)2 ]- and Y-shaped [CN(HCN)3 ]- molecular ions in the crystal. Both anions can be considered members of highly labile cyanide-HCN solvates of the type [CN(HCN)n ]- (n=1, 2, 3 …) as well as formal polypseudohalide ions.

SUBMITTER: Blasing K

PROVIDER: S-EPMC7317722 | biostudies-literature | 2020 Jun

REPOSITORIES: biostudies-literature

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Salts of HCN-Cyanide Aggregates: [CN(HCN)2 ]- and [CN(HCN)3 ].

Bläsing Kevin K Harloff Jörg J Schulz Axel A Stoffers Alrik A Stoer Philip P Villinger Alexander A

Angewandte Chemie (International ed. in English) 20200421 26

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=Ph4 P, Ph3 PNPPh3 =PNP) was investigated. Depending on the cation, it was possible to extract salts containing the formal dihydrogen tricyanide [CN(HCN)2 ]- and trihydrogen tetracyanide ions [CN(HCN)3 ]- from ...[more]

PMID: 32027458

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Project description:The title compounds, catena-poly[[[bis-[(R)-propane-1,2-di-amine-κ(2) N,N']copper(II)]-μ-cyanido-κ(2) N:C-[tris-(cyanido-κC)(nitroso-κN)iron(III)]-μ-cyanido-κ(2) C:N] monohydrate], {[Cu(Lpn)2][Fe(CN)5(NO)]·H2O} n , (I), and poly[[hexa-μ-cyanido-κ(12) C:N-hexa-cyanido-κ(6) C-hexa-kis-[(R)-propane-1,2-di-amine-κ(2) N,N']dichromium(III)tricopper(II)] penta-hydrate], {[Cu(Lpn)2]3[Cr(CN)6]2·5H2O} n , (II) [where Lpn = (R)-propane-1,2-di-amine, C3H10N2], are new chiral cyanide-bridged bimetallic coordination polymers. The asymmetric unit of compound (I) is composed of two independent cation-anion units of {[Cu(Lpn)2][Fe(CN)5)(NO)]} and two water mol-ecules. The Fe(III) atoms have distorted octa-hedral geometries, while the Cu(II) atoms can be considered to be penta-coordinate. In the crystal, however, the units align to form zigzag cyanide-bridged chains propagating along [101]. Hence, the Cu(II) atoms have distorted octa-hedral coordination spheres with extremely long semicoordination Cu-N(cyanido) bridging bonds. The chains are linked by O-H⋯N and N-H⋯N hydrogen bonds, forming two-dimensional networks parallel to (010), and the networks are linked via N-H⋯O and N-H⋯N hydrogen bonds, forming a three-dimensional framework. Compound (II) is a two-dimensional cyanide-bridged coordination polymer. The asymmetric unit is composed of two chiral {[Cu(Lpn)2][Cr(CN)6]}(-) anions bridged by a chiral [Cu(Lpn)2](2+) cation and five water mol-ecules of crystallization. Both the Cr(III) atoms and the central Cu(II) atom have distorted octa-hedral geometries. The coordination spheres of the outer Cu(II) atoms of the asymmetric unit can be considered to be penta-coordinate. In the crystal, these units are bridged by long semicoordination Cu-N(cyanide) bridging bonds forming a two-dimensional network, hence these Cu(II) atoms now have distorted octa-hedral geometries. The networks, which lie parallel to (10-1), are linked via O-H⋯O, O-H⋯N, N-H⋯O and N-H⋯N hydrogen bonds involving all five non-coordinating water mol-ecules, the cyanide N atoms and the NH2 groups of the Lpn ligands, forming a three-dimensional framework.

Dataset Information

Salts of HCN-Cyanide Aggregates: [CN(HCN)2 ]- and [CN(HCN)3 ].

Publications

Salts of HCN-Cyanide Aggregates: [CN(HCN)<sub>2</sub> ]<sup>-</sup> and [CN(HCN)<sub>3</sub> ].

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