Issue 14, 2016

The role of imidoselenium(ii) chlorides in the formation of cyclic selenium imides via cyclocondensation

Abstract

The third member of the series of imidoselenium(II) chlorides ClSe[N(tBu)Se]nCl (n = 3) (9) has been isolated from the cyclocondensation reaction of tBuNH2 and SeCl2 in THF in a molar ratio of ca. 3 : 1 and characterized in the form of two polymorphs 9a and 9b by single crystal X-ray analysis. The unusual structural features of this nine-atom chain are explained satisfactorily in terms of a bonding model that invokes intra-molecular secondary bonding interactions and hyperconjugation. The reaction of the bifunctional reagent ClSe[N(tBu)Se]2Cl (8) with tBuNH2 in THF occurs via concurrent pathways to give 1,3,5-Se3(NtBu)3 (1) and 1,3-Se3(NtBu)2 (3a). The energetics of the reactions of tBuNH2 and SeCl2 in THF have been calculated at the PBE0/def2-TZVPP level of theory in order to assess the feasibility of ClSe[N(tBu)Se]nCl (7–9, n = 1–3) as intermediates in the formation of known cyclic selenium imides. DFT calculations were also employed to explore the energy profile of the pathway of the formation of the first member of the series ClSeN(tBu)SeCl (7) from tBuNH2 and SeCl2 in THF at 298 K. The neutral ligand ClSeN(tBu)SeCl (7) is Se,Se′-coordinated to the metal centre in the unusual adduct [PdCl2{Se,Se′-(SeCl)2N(tBu)}]·[PdCl2{Se,Se′-Se4(NtBu)3}]·MeCN (10·MeCN), which is the first metal complex of an imidoselenium(II) chloride.

Graphical abstract: The role of imidoselenium(ii) chlorides in the formation of cyclic selenium imides via cyclocondensation

Supplementary files

Article information

Article type
Paper
Submitted
28 okt 2015
Accepted
20 nov 2015
First published
24 nov 2015

Dalton Trans., 2016,45, 6210-6221

The role of imidoselenium(II) chlorides in the formation of cyclic selenium imides via cyclocondensation

A. J. Karhu, O. J. Pakkanen, J. M. Rautiainen, R. Oilunkaniemi, T. Chivers and R. S. Laitinen, Dalton Trans., 2016, 45, 6210 DOI: 10.1039/C5DT04236D

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