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Cyclopalladation to form Planar Tridentate [ N-C-N] - Intramolecular Coordination Systems involving Pyridine Donor Groups, including Ligand Synthesis and X-Ray Structural Studies

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Canty, AJ and Minchin, NJ and Skelton, BW and White, AH (1987) Cyclopalladation to form Planar Tridentate [ N-C-N] - Intramolecular Coordination Systems involving Pyridine Donor Groups, including Ligand Synthesis and X-Ray Structural Studies. Journal of the Chemical Society, Dalton Transactions, 6. pp. 1477-1483. ISSN 1477-9226

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Abstract

Reaction of palladium(II) acetate with l,3-bis[l - (pyridin-2-yl)ethyl] benzene and 1,3- bis(2-pyridinecarbonyl) benzene results in cyclopalladation and formation of 2,6-bis[l-(pyridin-2-yl)ethyl] phenyl and 2,6-bis(2-pyridinecarbonyl)phenyl complexes [Pd{(NC5H4CHMe)2C6H3}(O2CMe)].1.5H2O (1) and [Pd{(NC5H4CO)2C6H3}(O2CMe)] (4), respectively. X- Ray crystallographic studies reveal square-planar co-ordination and unidentate acetate groups, with tridentate [N-C-N]- intramolecular co-ordination involving two six-membered palladocycle rings. Proton n.m.r. spectra of complex (1) and its chloro-derivative [Pd{(NC5H4CHMe)2C6H3}Cl] (2) indicate the presence of meso and rac diastereoisomers, but the crystal of (1) used for X-ray study contained the meso form only [monoclinic, space group C2/c with a = 26.08(1 ), b = 11.093(6), c = 15.846(7) A, beta = 116.19(3), and Z = 8; R = 0.042 for 2909 'observed' reflections]. Crystals of (4) contain two molecules in the asymmetric unit, with the molecules having different conformations of the tridentate ligand [monoclinic, space group Pc with a = 11.373(6), b = 10.925(6), c = 15.640(10) A, beta = 11 6.98(4), Z = 4; R = 0.043 (both chiralities) for 2677 'observed' reflections]. Syntheses of the new ligands are described.

Item Type: Article
Journal or Publication Title: Journal of the Chemical Society, Dalton Transactions
Page Range: pp. 1477-1483
ISSN: 1477-9226
Identification Number - DOI: 10.1039/DT9870001477
Date Deposited: 10 Jan 2008 21:50
Last Modified: 18 Nov 2014 03:26
URI: http://eprints.utas.edu.au/id/eprint/2817
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