Arsenic-Mediated C-C Coupling of Cyanides Leading to Cyanido Arsazolide [AsC4 N4 ]

Sören Arlt; Jörg Harloff; Axel Schulz; Alrik Stoffers; Alexander Villinger

doi:10.1002/chem.201703317

Arsenic-Mediated C-C Coupling of Cyanides Leading to Cyanido Arsazolide [AsC₄ N₄ ]

Chemistry. 2017 Sep 18;23(52):12735-12738. doi: 10.1002/chem.201703317. Epub 2017 Aug 18.

Authors

Sören Arlt¹, Jörg Harloff¹, Axel Schulz^{1

2}, Alrik Stoffers¹, Alexander Villinger¹

Affiliations

¹ Institut für Chemie, Universität Rostock, Albert-Einstein-Straße 3 a, 18059, Rostock, Germany.
² Leibniz-Institut für Katalyse e.V. an der Universität Rostock, Albert-Einstein-Straße 29 a, 18059, Rostock, Germany.

PMID: 28833758
DOI: 10.1002/chem.201703317

Abstract

The chemistry of arsenic cyanides has been investigated and is found to be completely different to the chemistry of the heavier analogs antimony and bismuth as well as phosphorus. The reaction of As(CN)₃ with cyanide salts resulted in the formation of an unknown cyanido arsazolide heterocycle, which represents a structure isomer of the desired [As(CN)₄ ]^- . The structure, bonding, and formation of this unusual heterocycle is discussed featuring an arsenic mediated C-C coupling of cyanides. [AsC₄ N₄ ]^- salts with different counterions such as [PPh₄ ]⁺ , [PPN]⁺ =[Ph₃ P-N-PPh₃ ]⁺ , Ag⁺ , and [BMIm]⁺ are reported with [BMIm][AsC₄ N₄ ] being a low-temperature ionic liquid (T_m =-62 °C).

Keywords: C−C coupling; arsenic; cyanides; heterocycles; isomerization.