Issue 33, 2011
From the journal:

Dalton Transactions

The solution stability of copper(i) and silver(i) complexes with N-heterocyclic carbenes†

Valeria Amendola,a   Greta Bergamaschi,a   Massimo Boiocchi,b   Luigi Fabbrizzi*a  and  Nadia Fuscoa  

* Corresponding authors

a Dipartimento di Chimica Generale, Università di Pavia, via Taramelli 12, Pavia, Italy
E-mail: luigi.fabbrizzi@unipv.it
Fax: +39 0382 528544
Tel: +39 0382 987328

b Centro Grandi Strumenti, Università di Pavia, via Ugo Bassi, Pavia, Italy

Abstract

The tris-benzimidazolium cage LH33+, in MeCN solution, in the presence of OH−, forms with CuI and AgI ions complexes of formula [MI(LH)]2+, in which each metal is linearly coordinated by two carbenes and one imidazolium N–H fragment remains intact. To achieve two-coordination, the two N-heterocyclic moieties of the cage make a saloon-door type motion, with a conformationally costless rotation of ca. 30° each. The two [MI(LH)]2+ complexes show high thermodynamic stability and are inert with respect to metal substitution, due to the mechanical constraints imposed by the ligating framework. Complexation with CuI and AgI with the reference unidentate carbene ligand Q, derived from the benzimidazolium precursor QH+, was studied for comparison. Both metals in MeCN form 1 : 1 and 1 : 2 complexes with the carbene ligand Q according to two stepwise equilibria. Q complexes of both metals are labile with respect to metal substitution and those of AgI are more stable than those of CuI. A significant cooperative effect has been observed with the formation of the [AgIQ2]+ complex.

Graphical abstract: The solution stability of copper(i) and silver(i) complexes with N-heterocyclic carbenes

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Article information

DOI
https://doi.org/10.1039/C1DT10894H
Article type
Paper
Submitted
12 May 2011
Accepted
01 Jun 2011
First published
19 Jul 2011

Dalton Trans., 2011,40, 8367-8376

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The solution stability of copper(I) and silver(I) complexes with N-heterocyclic carbenes

V. Amendola, G. Bergamaschi, M. Boiocchi, L. Fabbrizzi and N. Fusco, Dalton Trans., 2011, 40, 8367 DOI: 10.1039/C1DT10894H

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