Issue 10, 2012

2,2′:6′,2′′-Terpyridine substituted in the 4′-position by the solubilizing and sterically demanding tert-butyl group: a surprisingly new ligand

Abstract

We describe the synthesis and characterization of 4′-tert-butyl-2,2′:6′,2′′-terpyridine (4′-tButpy, 1), a convergent tpy ligand that exhibits both a sterically demanding and solubilizing 4′-substituent. In the solid state, molecules of 1 pack with alternating tpy and tert-butyl domains, and the bulky alkyl substituents prevent the molecules from engaging in the face-to-face π-interactions which are typical of simple tpy ligands. Instead, the predominant packing forces involve CH⋯N hydrogen bonds and weak CH⋯π contacts. The syntheses of the homoleptic complexes [M(1)2][PF6]2 (M = Fe, Co, Zn and Ru) and the heteroleptic [Ru(tpy)(1)][PF6]2 are described. The complexes have been fully characterized in solution, including the 1H NMR spectroscopic characterization of the paramagnetic [Co(1)2][PF6]2. Cyclic voltammetric data are consistent with the tert-butyl substituent being slightly electron releasing. The single crystal structures of [Zn(1)2][PF6]2 and [Ru(1)2][PF6]2 have been determined; the compounds are essentially isomorphous. The packing of the cations is such that the tert-butyl substituents are accommodated in pockets between the tpy domains of adjacent cations, and as a consequence, the {M(tpy)2}-embrace that is a ubiquitous feature of many related structures is not observed.

Graphical abstract: 2,2′:6′,2′′-Terpyridine substituted in the 4′-position by the solubilizing and sterically demanding tert-butyl group: a surprisingly new ligand

Supplementary files

Article information

Article type
Paper
Submitted
09 Nov 2011
Accepted
08 Dec 2011
First published
23 Jan 2012

Dalton Trans., 2012,41, 2890-2897

2,2′:6′,2′′-Terpyridine substituted in the 4′-position by the solubilizing and sterically demanding tert-butyl group: a surprisingly new ligand

E. C. Constable, N. Hostettler, C. E. Housecroft, P. Kopecky, M. Neuburger and J. A. Zampese, Dalton Trans., 2012, 41, 2890 DOI: 10.1039/C2DT12142E

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