Complexes between copper(I) chloride and polydentate aromatic amines Bjo ¨ rn Gustafsson a , Mikael Ha ˚kansson b , Susan Jagner a, * a Department of Inorganic Chemistry, Chalmers University of Technology, SE-41296 Go ¨teborg, Sweden b Organic Chemistry, Department of Chemistry, Go ¨teborg University, SE-41296 Go ¨teborg, Sweden Received 20 June 2002; accepted 2 October 2002 Dedicated to Prof. Dr. Pierre Braunstein Abstract Two compounds containing polydentate aromatic amines have been prepared and characterised by means of crystal structure determination. Compound 1, catena -m-chloro-m-1,4-phenylenediamine-(acetonitrile)copper(I), is an infinite polymeric chain in which copper(I) is bridged alternately by the amine and by chloride. Compound 2, bis[tris(4-aminophenyl)amine](acetonitrile)chlor- ocopper(I), is a discrete monomer, neutral monomeric complexes being unusual among aminochlorocopper(I) compounds. Moreover, 2 would seem to be the first metal complex containing tris(4-aminophenyl)amine as a ligand whose structure has been determined. copper(I) exhibits distorted tetrahedral coordination geometry in both complexes. Whereas 1 decomposes owing to loss of acetonitrile solvent immediately on exposure to the atmosphere, 2 is far more resistant to decomposition, the solvent molecule being protected by intramolecular and intermolecular pockets formed by the phenyl groups of the triphenylamine ligand. # 2003 Elsevier Science B.V. All rights reserved. Keywords: Copper(I); Chloride; 1,4-Phenylenediamine; Tris(4-aminophenyl)amine; Acetonitrile; Crystal packing 1. Introduction The properties and rich structural chemistry of haloaminecopper(I) complexes have been described in a comprehensive review [1]. Further investigations, since then, include the incorporation of ligands containing N- and both N- and P-donors into halocuprate (I) species [2]. There has been considerable focus, which has accelerated in recent years, on complexes between copper(I) and tripodal amines with pendant aromatic arms, often pyridine-based, as biomimetic models in connection with the uptake of dioxygen [3]. Thus, protective pockets with a free coordination site for attack by dioxygen have been designed, and such entities have, moreover, been shown to be useful templates for the stabilisation of unusual coordination geometries of the copper(II) cation [4]. Our interest in this field stemmed from investigation of complexes between copper(I) and hard donors such as oxygen and the reactivity of such complexes with respect to carbonylation [5]. Somewhat surprisingly, however, there appears to be a lack of structural information concerning complexes between copper(I) and simple aromatic diamines such as the phenylene- diamines, or triphenylamine. We have therefore at- tempted to prepare complexes between copper(I) chloride and phenylenediamine, succeeding to isolate a complex with p -phenylenediamine. In order to further investigate preferential bonding with respect to different nitrogen sites, we prepared a ligand with three pendant aminophenyl donors, viz. tris(4-aminophenyl)amine and examined its reactivity towards copper(I) chloride. We here report the preparation and structural characterisa- tion of the novel complexes, catena -m-chloro-m- 1,4-phenylenediamine-(acetonitrile)copper(I) (1) and bis[tris(4-aminophenyl)amine](acetonitrile)-chlorocop- per(I) (2), depicted in Schemes 1 and 2, respectively. * Corresponding author. Tel.:  /46-31-772 2852; fax:  /46-31-772 2846. E-mail address: susan@inoc.chalmers.se (S. Jagner). Inorganica Chimica Acta 350 (2003) 209  /214 www.elsevier.com/locate/ica 0020-1693/03/$ - see front matter # 2003 Elsevier Science B.V. All rights reserved. doi:10.1016/S0020-1693(02)01548-7