758705-88-3Relevant academic research and scientific papers
Arylaminopyridinato complexes of zirconium
Crust, Edward J.,Munslow, Ian J.,Morton, Colin,Scott, Peter
, p. 2257 - 2266 (2007/10/03)
A range of 2-arylaminopyridines (HL) are synthesised readily from bromopyridines and amines using palladium-catalysed animation. Protonolysis reactions of these proligands with ZrX4 (X = NMe2, CH 2Ph, 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.
