UNSPECIFIED. (2004) Arylaminopyridinato complexes of zirconium. DALTON TRANSACTIONS (15). pp. 2257-2266. ISSN 1477-9226

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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 pi-pi stacking, even when bulky arene substituents are employed at L. This leads to the complexes adopting a C-2v-symmetric core; (iii) the amides [ZrL2(NMe2)(2)] have structures for which aromatic pi-pi stacking is unfeasible, and correspondingly C-2-symmetric or similar structures are adopted. All the structural data presented is consistent with a trans influence order at zirconium Me2N > RCH2 > py.

Item Type:	Journal Article
Subjects:	Q Science > QD Chemistry
Journal or Publication Title:	DALTON TRANSACTIONS
Publisher:	ROYAL SOC CHEMISTRY
ISSN:	1477-9226
Date:	2004
Number:	15
Number of Pages:	10
Page Range:	pp. 2257-2266
Identification Number:	10.1039/b407008a
Publication Status:	Published
URI:	http://wrap.warwick.ac.uk/id/eprint/8182

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