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 十月 2015
Accepted
20 十一月 2015
First published
24 十一月 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

To request permission to reproduce material from this article, please go to the Copyright Clearance Center request page.

If you are an author contributing to an RSC publication, you do not need to request permission provided correct acknowledgement is given.

If you are the author of this article, you do not need to request permission to reproduce figures and diagrams provided correct acknowledgement is given. If you want to reproduce the whole article in a third-party publication (excluding your thesis/dissertation for which permission is not required) please go to the Copyright Clearance Center request page.

Read more about how to correctly acknowledge RSC content.

Social activity

Spotlight

Advertisements