Chalcogen-nitrogen Chemistry: From Fundamentals To Applications In Biological, Physical And Materials Sciences (Updated Edition) by Tristram Chivers;Risto S Laitinen;

Author:Tristram Chivers;Risto S Laitinen;
Language: eng
Format: epub
Publisher: World Scientific Publishing Company
Published: 2022-06-15T00:00:00+00:00

Chart 8.10. Mixed tellurium/sulfur-nitrogen halides and the [Te2S2N4]2+ dication.

8.11 Imidochalcogen(II) Halides

Comprehensive investigations of the cyclocondensation reactions of tertbutylamine with SeCl2 using different stoichiometries have resulted in the isolation and characterisation of a homologous series of acyclic imidoselenium(II) dichlorides ClSe[N(tBu)Se]nCl (n = 1–3) (Fig. 8.1).73−76 There are no sulfur or tellurium analogues of this class of chalcogennitrogen halides.

As illustrated in Fig. 8.1b, there is a close ClSe∙∙∙SeCl contact of 2.891 Å (cf. sum of van der Waals radii for Se and Cl is 4.0 Å) in ClSe[N(tBu)Se]2Cl, which is accompanied by a pronounced alternation in the Se–N distances (1.803 and 1.948 Å) and, to a smaller extent, the Se–Cl (2.313 and 2.269 Å) bond lengths.75 These structural observations can be explained by two lone pair (N) → σ*(Se–Cl) interactions as depicted in Fig. 8.2. The intramolecular ClSe∙∙∙SeCl interaction is much weaker in the two polymorphs of the longer chain ClSe[N(tBu)Se]3Cl (3.345 and 3.368 Å).76

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