Synthesis and nuclear magnetic resonance investigation of 1-phenylpropane-1,2-dione 2-oxime complexes of trimethylplatinum(IV)

Author(s): Heard Peter J. | Kite Kenneth.

Type of publication: Journal paper

Abstract: The ionised monoxime 1-phenylpropane-1,2-dione 2-oximate (ppdm) reacted smoothly with trimethylplatinum(IV) sulfate in aqueous acetone to form the complex fac-[PtMe3(ppdm)(H2O)]1 in high yield. Complex 1 reacted with 3,5-dimethylpyridine (dmpy) and 2,2′-bipyridine (bipy) to form stable 1 : 1 adducts, viz. fac-[PtMe3(ppdm)(dmpy)]2 and fac-[PtMe3(ppdm)(bipy)]3. In complexes 1 and 2 the ionised monoxime behaves as a N,O bidentate chelate, whereas in 3 ppdm is co-ordinated to the metal in a monodentate fashion, via the N-donor atom. The parent complex 1 dissolves in polar solvents to form species of general formulae fac-[PtMe3(ppdm)(solv)](solv = Me2SO, methanol or acetone), which undergo an intramolecular ‘windscreenwiper’ fluxional rearragement. The stereodynamics of the fluxional process have been measured in CD3OD and (CD3)2SO 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.

Published URL: https://pubs.rsc.org/en/content/articlelanding/1996/dt/dt9960003543#!

Date Published: April 25 1996

Publisher: The Royal Society of Chemistry

Place of publication: London (United Kingdom)

Pages: 3543-3548

Subject(s): Chemistry

DOI: https://doi.org/10.1039/DT9960003543

Keywords: 1-phenylpropane-1 | 2-dione 2-oxime | trimethylplatinum(IV

Depositing User: Luke Miller