Issue 19, 2014

The surprising lability of bis(2,2′:6′,2′′-terpyridine)chromium(iii) complexes

Abstract

The complex [Cr(tpy)(O3SCF3)3] (tpy = 2,2′:6′,2′′-terpyridine) is readily made from [Cr(tpy)Cl3] and is a convenient precursor to [Cr(tpy)2][PF6]3 and to [Cr(tpy)(4′-(4-tolyl)tpy)][PF6]3 and [Cr(tpy)(5,5′′-Me2tpy)][PF6]3 (4′-(4-tolyl)tpy = 4′-(4-tolyl)-2,2′:6′,2′′-terpyridine; 5,5′′-Me2tpy = 5,5′′-dimethyl-2,2′:6′,2′′-terpyridine); these are the first examples of heteroleptic bis(tpy) chromium(III) complexes. The single crystal structures of 2{[Cr(tpy)2][PF6]3}·5MeCN, [Cr(tpy)(4′-(4-tolyl)tpy)][PF6]3·3MeCN and [Cr(tpy)(5,5′′-Me2tpy)][PF6]3·3MeCN have been determined. Each cation contains the expected octahedral {Cr(tpy)2}3+ unit; in all three structures, the need to accommodate three anions per cation and the solvent molecules prevents the formation of a grid-like array of cations that is typical of many lattices containing {M(tpy)2}2+ motifs. Three reversible electrochemical processes are observed for [Cr(tpy)(4′-(4-tolyl)tpy)][PF6]3 and [Cr(tpy)(5,5′′-Me2tpy)][PF6]3, consistent with those documented for [Cr(tpy)2]3+. At pH 6.36, aqueous solutions of [Cr(tpy)2][PF6]3 are stable for at least two months. However, contrary to the expectations of the d3 Cr3+ ion being a kinetically inert metal centre, the tpy ligands in [Cr(tpy)2]3+ are labile in the presence of base; absorption and 1H NMR spectroscopies have been used to monitor the effects of adding NaOH to aqueous and CD3OD solutions, respectively, of the homo- and heteroleptic complexes. Ligand dissociation is also observed when [Bu4N]F is added to CD3OD solutions of the complexes, but in aqueous solution, [Cr(tpy)2][PF6]3 is stable in the presence of fluoride ion.

Graphical abstract: The surprising lability of bis(2,2′:6′,2′′-terpyridine)chromium(iii) complexes

Supplementary files

Article information

Article type
Paper
Submitted
20 Jan 2014
Accepted
24 Mar 2014
First published
31 Mar 2014
This article is Open Access
Creative Commons BY license

Dalton Trans., 2014,43, 7227-7235

Author version available

The surprising lability of bis(2,2′:6′,2′′-terpyridine)chromium(III) complexes

E. C. Constable, C. E. Housecroft, M. Neuburger, J. Schönle and J. A. Zampese, Dalton Trans., 2014, 43, 7227 DOI: 10.1039/C4DT00200H

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