3-DIPHENYLPHOSPHINO-(1R)-(+)-CAMPHOR DIMETHYLHYDRAZONE COMPLEXES WITH PLATINUM(II) AND PALLADIUM(II)

Treatment of the Z-exo-phosphine PPh2C10H15NNMe2 1a with [PdCl2(NCPh)2] or Na2[PdCl4].4H2O gives the compound [activated PdCl2(activated PPh2C10H15NNMe2)] 2a with the PPh2 group exo and the C = NNMe2 configuration Z, i.e. a six-membered ring chelate complex. The corresponding platinum complex 2d was made from 1a and [PtCl2(cod)] (cod = cycloocta-1,5-diene). Metathesis of complex 2a or 2d with LiBr, or 2a with Nal, gave the corresponding bromides or iodide. Treatment of 2d with AgNO3 gave the mononitrato complex [activated PtCl(ONO2)(activated PPh2C10H15NNMe2)] 2f. Treatment of [PtMe2(cod)] with 1a gave [activated PtMe2(activated PPh2C10H15NNMe2)] 2g. The exo-phosphine 1a when treated with acetic acid or hot sodium ethoxide solution was partially converted into a mixture with the corresponding endo-phosphine 1b. Treatment of [PtCl2(cod)] with the 1a-1b mixture gave a mixture of the Z-exo-/endo-chelate complexes [activated PtCl2(activated PPh2C10H15NNMe2)]; similar treatment of [PdCl2(NCPh)2] or [PtMe2(cod)] gave the corresponding exo-/endo-complexes. Treatment of 2d with hydrogen chloride gave a new (protonated) species which with ethanol gave the exo-/endo-mixture 2d-3a. The palladium complex 2a with hydrogen chloride followed by methanol gave 2a-3b. and another complex formulated as E-exo-[activated PdCl2(activated PPh2C10H15NNMe2)] 5. Treatment of 2d with an excess of LiMe gave a new species formulated as an anion [activated PtMe2(activated PPh2C10H14NNMe2)]- 4, which with methanol gave the exo-/endo-mixture 2g-3c. Proton, C-13-{H-1} and P-31-{H-1} NMR data are given and discussed in some detail particularly regarding the determination of the stereochemistry at C(3) on the camphor residue. Crystals of compound 2a are orthorhombic, space group P2(1)2(1)2(1) with a = 1165.1(2), b = 1272.5(2), c = 2106.1 (5) pm and Z = 4; final R factor 0.0421 for 2812 observed reflections. The structure shows that the co-ordinated PPh2 group is on the 3-exo position whilst the C = NNMe2 moiety is coordinated through the NMe2 nitrogen giving a six-membered co-ordinated ring. The arrangement around C = N is Z.