Issue 15, 2004

Arylaminopyridinato complexes of zirconium

Abstract

A range of 2-arylaminopyridines (HL) are synthesised readily from bromopyridines and amines using palladium-catalysed amination. Protonolysis reactions of these proligands with ZrX4 (X = NMe2, CH2Ph, CH2But) yield zirconium complexes of the type [MLnX4−n], several of which have been characterised by X-ray crystallography. Control of metal/ligand stoichiometry and structure is pursued by investigation of the effects on substitution patterns of the pyridine and aryl rings. Some distinct patterns emerged; (i) the 6-methyl position on the pyridine appears to be particularly important with regards to control of stoichiometry, although there are co-ligand effects; (ii) structures of the metal alkyl derivatives [ZrLn(CH2R)4−n] are dominated by aromatic π–π stacking, even when bulky arene substituents are employed at L. This leads to the complexes adopting a C2v-symmetric core; (iii) the amides [ZrL2(NMe2)2] have structures for which aromatic π–π stacking is unfeasible, and correspondingly C2-symmetric or similar structures are adopted. All the structural data presented is consistent with a trans influence order at zirconium Me2N > RCH2 > py.

Graphical abstract: Arylaminopyridinato complexes of zirconium

Article information

Article type
Paper
Submitted
10 May 2004
Accepted
10 Jun 2004
First published
29 Jun 2004

Dalton Trans., 2004, 2257-2266

Arylaminopyridinato complexes of zirconium

E. J. Crust, I. J. Munslow, C. Morton and P. Scott, Dalton Trans., 2004, 2257 DOI: 10.1039/B407008A

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