Comments

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://www.rsc.org

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.

Disciplines

Chemistry | Inorganic Chemistry | Organic Chemistry | Physical Chemistry

Recommended Citation

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