Issue 14, 2016

Bis-(benzothiazol-2-yl)-amines and their metal amides: a structural comparison in the solid state

Abstract

Within this work, the field of amide ligand platforms for group 13 metal complexation, especially for Al(III) is investigated in a synthetic as well as in a structural comparative approach. Starting from bis-heterocyclo methanides, which mimic the omnipresent nacnac ligand, the next enhancement in this class of ligands includes the exchange of the central methylene bridge by an amine nitrogen atom. With this modification three different sec. amines, each symmetrically substituted, could be synthesised as parent neutral benzothiazole containing ligand systems: (NCSC6H4)2NH (1), (4-MeNCSC6H3)2NH (2) and (4-OMeNCSC6H3)2NH (3). Apart from these compounds also a lithiated species and a row of group 13 metal complexes of the deprotonated ligands could be examined by applying single crystal X-ray diffraction analyses. In this course three new dimethyl aluminium containing complexes [Me2Al{(NCSC6H4)2N}] (4), [Me2Al{(4-MeNCSC6H3)2N}] (5) and [Me2Al{(4-OMeNCSC6H3)2N}·AlMe3] (6) as well as two lithiated compounds [Li{(NCSC6H4)2N}]4 (7), [Li{(4-MeNCSC6H3)2N}]4 (8) were structurally and spectroscopically characterised. A subsequent structural comparison of 1–6 and 8 in the solid state shows that the parent ligand systems prefer a planar cis-trans alignment due to hydrogen bond formation. In contrast to that, the metallated species favour a planar but transtrans or ciscis alignment depending on the metal cation.

Graphical abstract: Bis-(benzothiazol-2-yl)-amines and their metal amides: a structural comparison in the solid state

Supplementary files

Article information

Article type
Paper
Submitted
06 Okt 2015
Accepted
19 Nov 2015
First published
19 Nov 2015
This article is Open Access
Creative Commons BY license

Dalton Trans., 2016,45, 6136-6148

Author version available

Bis-(benzothiazol-2-yl)-amines and their metal amides: a structural comparison in the solid state

David-R. Dauer, M. Flügge, R. Herbst-Irmer and D. Stalke, Dalton Trans., 2016, 45, 6136 DOI: 10.1039/C5DT03911H

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