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DOI: 10.1039/A809179J (Paper) Reference Section for: J. Chem. Soc., Dalton Trans., 1999, 923-930

Co-ordination chemistry of CuI with 1,3,5-tris[bis(pyridin-2-ylmethyl)aminomethyl]-2,4,6-triethylbenzene, a conformationally constrained trinucleating ligand

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Christian Walsdorff, Sunyoung Park, Jeongho Kim, Jungseok Heo, Ki-Min Park, Jinho Oh and Kimoon Kim

Abstract

The new ligand 1,3,5-tris[bis(pyridin-2-ylmethyl)aminomethyl]-2,4,6-triethylbenzene (L) was prepared from 1,3,5-tris(bromomethyl)-2,4,6-triethylbenzene (TriBr) and bis(pyridin-2-ylmethyl)amine. In the crystal state TriBr adopts a conformation with the substituents alternately pointing to opposite sides of the plane of the benzene ring. Compound L adopts a similar conformation. With its donor sets thus coming together on the same side of the benzene ring L can co-ordinate three copper(I) species in a defined and close proximity. This is illustrated by the crystal structures of L, [(CuI)3L] and [(CuNCMe)3L][PF6]3. The electrochemical interdependence of the copper centres in [(CuI)3L] and [(CuBr)3L] has been investigated by cyclic voltammetry. With weaker and harder terminal ligands such as acetonitrile the [CuI3L]3+ species in CH2Cl2 are liable to oxidation by the solvent to give CuIICl+ species. In one such degradation product L co-ordinates besides an isolated CuI, a CuI and a CuII bridged by a single chloride. The CuII is further co-ordinated by an oxygen from a perchlorate anion. From the reaction of only two equivalents of [Cu(NCMe)4]BF4 with L a dinuclear compound was obtained, in which both copper atoms experience a distorted trigonal co-ordination from three pyridine nitrogen atoms each.

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