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.
Chemistry | Inorganic Chemistry | Organic Chemistry | Physical Chemistry
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
Digital Commons Citation
Heard, Peter J. and Kite, Kenneth, "Synthesis And NMR Investigation of 1-Phenyl-1,2-propanedione-2-oxime Complexes of Trimethylplatinum(IV)." (1996). Chemistry. Paper 12.