Synthesis And NMR Investigation of 1-Phenyl-1,2-propanedione-2-oxime Complexes of Trimethylplatinum(IV).

Heard, Peter J and Kite, Kenneth (1996) Synthesis And NMR Investigation of 1-Phenyl-1,2-propanedione-2-oxime Complexes of Trimethylplatinum(IV).

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Abstract

The ionised monoxime, 1-phenyl-1,2-propanedione-2-oxime (ppdm) reacts smoothly with trimethylplatinum(IV) sulfate in aqueous acetone, to form the complex fac-[PtMe₃ (ppdm)(H₂O)] 1 in high yield. 1 Reacts with 3,5-lutidine and 2,2'-bipyridine to form stable 1:1 adducts, viz. fac-[PtMe₃(ppdm)(3,5-lut)] 2 and fac-[PtMe₃(ppdm)(bipy)] 3. In complexes 1 and 2, the ionised monoxime behaves in a N/O bidentate chelate fashion, whereas in 3, ppdm is co-ordinated to the metal moiety in a monodentate fashion, via the oximate N donor atom. The parent complex, 1, dissolves in polar solvents to form species of general formulae fac-[PtMe₃(ppdm)(solv)] (solv = DMSO, methanol or acetone), which undergo an intramolecular "windscreen-wiper" fluxional rearrangement. The stereodynamics of the fluxional process have been measured in CD₃OD and [D₆]DMSO solution by two-dimensional exchange spectroscopy; ΔG‡ (298 K) is 73.6 kJ mol⁻¹ and 88.5 kJ mol⁻¹, respectively. The effects of the solvent on the energetics and a possible mechanism for the fluxional process are discussed.

Item Type: Article
Additional Information: Copyright © 1996 RCS, and reproduced here by permission of The Royal Society of Chemistry (RSC).This is the author's final draft after peer review, without figures. The article was published in Heard, P. J. and Kite, K., (1996) 'Synthesis And NMR Investigation of 1-Phenyl-1,2-propanedione-2-oxime Complexes of Trimethylplatinum(IV)'. Dalton Transactions, 3543-3548 by the Royal Society of Chemistry and is available online at http://dx.doi.org/10.1039/DT9960003543
Keywords: Trimethylplatinum(IV) complexes, Oxime ligands, Dynamic NMR, Spectroscopy, Windscreen-wiper mechanism
Divisions: ?? GlyndwrUniversity ??
Depositing User: ULCC Admin
Date Deposited: 05 Oct 2011 09:13
Last Modified: 11 Dec 2017 20:05
URI: http://glyndwr.repository.guildhe.ac.uk/id/eprint/150

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