Issue 17, 2012
From the journal:

Dalton Transactions

Synthesis and structural characterisation of (aryl-BIAN)copper(i) complexes and their application as catalysts for the cycloaddition of azides and alkynes†

Lidong Li,a   Patrícia S. Lopes,a   Vitor Rosa,b   Cláudia A. Figueira,a   M. Amélia N. D. A. Lemos,c   M. Teresa Duarte,a   Teresa Avilés*b  and  Pedro T. Gomes*a  

* Corresponding authors

a Centro de Química Estrutural, Departamento de Engenharia Química, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal
E-mail: pedro.t.gomes@ist.utl.pt
Fax: +351 218419612
Tel: +351 218419612

b REQUIMTE, Departamento de Química, Faculdade de Ciências e Tecnologia, Universidade Nova de Lisboa, Caparica 2829-516, Portugal
E-mail: tap@dq.fct.unl.pt
Fax: +351 212948550
Tel: +351 212948559

c Instituto de Biotecnologia e Bioengenharia, Centro de Engenharia Biológica e Química, Instituto Superior Técnico, Universidade Técnica de Lisboa, Av. Rovisco Pais, 1049-001 Lisboa, Portugal

Abstract

A series of Ar-BIAN-based copper(I) complexes (where Ar-BIAN = bis(aryl)acenaphthenequinonediimine) were synthesised and characterised by 1H and 13C NMR spectroscopies, FT-IR spectroscopy, MALDI-TOF-MS spectrometry, cyclic voltammetry and single crystal X-ray diffraction. The bis-chelated complexes of general formula [Cu(Ar-BIAN)2]BF4 (where Ar = C6H5 (1), 4-iPrC6H4 (3), 2-iPrC6H4 (4)) were prepared by reaction of [Cu(NCMe)4]BF4 with two equivalents of the corresponding Ar-BIAN ligands, in dichloromethane, while the mono-chelated complexes of the type [Cu(Ar-BIAN)L2]BF4 (where Ar = 2,6-iPr2C6H3, L = PhCN (6); Ar = 4-iPrC6H4, L = PPh3 (7)) were readily accessible by treatment of [Cu(NCR)4]BF4 (R = Me, Ph) with one equivalent of the corresponding Ar-BIAN ligands in the absence or presence of two equivalents of PPh3, in the same solvent. The structures of complexes 3, 4, 6 and 7 were obtained by single crystal X-ray diffraction, showing distorted tetrahedral geometries around the copper centres in all cases. The electrochemical studies of these complexes and of the already reported [Cu(2,4,6-Me3C6H2-BIAN)2]BF4 (2) and [Cu(2,6-iPr2C6H3-BIAN)(NCMe)2] (5), demonstrated that the bis-chelated complexes 1–4 undergo a reversible one-electron reduction or oxidation processes on copper, while the mono-chelated complexes 5–7 show a partially reversible oxidation and an irreversible reduction feature. Both kinds of (Ar-BIAN)copper(I) complexes are active catalysts for the copper(I)-catalysed azide–alkyne cycloaddition reaction (CuAAC). Complex 7, bearing PPh3 ligands, exhibits the highest catalytic activity, which is comparable with that of the typical CuSO4–sodium ascorbate catalyst system.

Graphical abstract: Synthesis and structural characterisation of (aryl-BIAN)copper(i) complexes and their application as catalysts for the cycloaddition of azides and alkynes

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Article information

DOI
https://doi.org/10.1039/C2DT11854H
Article type
Paper
Submitted
01 Oct 2011
Accepted
16 Jan 2012
First published
07 Mar 2012

Dalton Trans., 2012,41, 5144-5154

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Synthesis and structural characterisation of (aryl-BIAN)copper(I) complexes and their application as catalysts for the cycloaddition of azides and alkynes

L. Li, P. S. Lopes, V. Rosa, C. A. Figueira, M. A. N. D. A. Lemos, M. T. Duarte, T. Avilés and P. T. Gomes, Dalton Trans., 2012, 41, 5144 DOI: 10.1039/C2DT11854H

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