Homoleptic Selenium Cyanides: Attempted Preparation of Se(CN)₄ and Redetermination of the Crystal Structure of Se(CN)₂

Abstract

The preparation of Se(CN) 4 was attempted by the reaction of SeF 4 with Me 3SiCN at low temperatures. However, selenium tetracyanide could not be detected by NMR spectroscopy; instead, the decomposition product Se(CN) 2 was isolated and its crystal structure was redetermined. In the structure of Se(CN) 2, layers are present with secondary Se...N interactions. The structure of Se(CN) 4 and its reductive decomposition reaction has been calculated at the MP2 level of theory.

An exploding N-isocyanide reagent formally composed of anthracene, dinitrogen and a carbon atom

“…1 H and 13 C NMR analysis of the products revealed formation of minor amounts of unidentified species, together with A and cyanogen (δ ( 13 C) = 95.2 ppm) as the major products. 33 In conclusion, synthesis and reactivity studies of N-isocyanide 1 allowed establishment of a proof of concept for the transfer of a lone carbon atom. Thermal decomposition of 1 led to cyanogen formation.…”

Chalcogen bonding interactions in organic selenocyanates: from cooperativity to chelation

“…2,3,10 The simplest and most convincing example was already identified years ago in Se(CN)2, 11 and revisited recently. 12 Its X-ray crystal structure (Fig. 1a) shows indeed two nitrogen atoms of neighboring molecules pointing toward the σ-holes of the selenium atom, with Se•••N intermolecular distances, 2.813 (9) and 2.835 7Å, well below the sum of the van der Waals radii (3.45 Å), and C-Se•••N angles close to linearity (166-170°).…”

The competition of Y⋯o and X⋯n halogen bonds to enhance the group V σ-hole interaction in the NCY⋯oPH3⋯NCX and OPH3⋯NCX⋯NCY (X, YF, Cl, and Br) complexes

“…The σ‐hole concept was introduced by Murray et al in 2007 for Group V and Group VI covalently bonded atoms, and it was introduced by Murray et al in 2009 for Group IV covalently bonded atoms . From then on, the σ‐hole concept is increasingly being invoked to interpret noncovalent interactions of Group IV–VI atoms …”