PREPARATION AND PROPERTIES OF METHYLPLATINUM FLUOROALKOXIDE AND PHENOXIDE COMPLEXES, PTME(OR)(PME3)2 AND PTME(OR)(HOR)(PME3)2 (R = CH(CF3)2, C6H5)

Reactions of cis-PtMe2(PMe3)2 with 1,1,1,3,3,3-hexafluoro-2-propanol in 1/1 and 1/2 ratios give cis-PtMe(OCH(CF3)2)(PMe3)2 (1) and its hydrogen-bonded alcohol adduct, cis-PtMe(OCH(CF3)2)(HOCH(CF3)2)(PMe3)2 (2), respectively. Complex 2 undergoes exchange of the fluoroalkoxide ligand on addition of phenol to give cis-PtMe(OC6H5)(PMe3)2 (3) or its phenol adduct, cis-PtMe(OC6H5)-(HOC6H5)(PMe3)2 (4), depending on the ratio of added phenol to the complex. IR and NMR data of 2 and 4 indicate the presence of OH ··· O hydrogen bonding between the alkoxide (or phenoxide) ligand and the associated alcohol (or phenol) both in the solid state and in solution. Thermodynamic parameters for the association of the HOCH(CF3)2 with 1 in toluene have been obtained by means of 1H NMR spectroscopy as ΔH° -5.1 kcal mol-1, ΔG° -2.6 kcal mol-1, and ΔS° -9.1 e. u. at 273 K. Reaction of 1 with CO at room temeprature gives cis-PtMe(COOCH(CF3)2)(PMe3)2 (7a) produced through CO insertion into the PtO bond as confirmed by 31P{1H} and 13C{1H} NMR spectroscopy. The cis complex 7a is isomerized into trans-PtMe(COOCH(CF3)2)(PMe3)2 (7b) under the reaction conditions. Reaction of the phenoxide complex 3 with CO does not cause insertion of CO into the PtO bond, and gives trans-PtMe(OPh)(PMe3)2. © 1990.