COMPLEXES OF THE BIDENTATE LIGANDS PPH2CH2C(BUT)=NNR2 (R = H OR ME) AND PPH2CH2C(BUT)=N-N=CHPH WITH PALLADIUM AND PLATINUM - X-RAY CRYSTAL-STRUCTURE OF CIS-[PT(PPH2CH2C(BUT)=NNH)2]

tert-Butyl diphenylphosphinomethyl ketone dimethylhydrazone L1 reacts with [PtCl2(cod)] (cod = cycloocta-1,5-diene) to give the chelate [PtC l2{PPh2CH2C(Bu(t))=NNMe2}] with a six-membered chelate ring; the corre sponding palladium complex was also prepared. The phosphino dimethylhy drazone L1 or the phosphino hydrazone L2 also react with [PtMe2(cod)] to give (PtMe2{PPh2CH2C(But)=NNR2}], (R = Me or H); these platinum(II) complexes react with methyl iodide to give the corresponding trimethy lplatinum(IV) complexes [PtMe3I{PPh2CH2C(But)=NNR2}]. Treatment of [Pt Cl2(cod)] with 2 equivalents of L2 gave the dication cis-[Pt{PPh2CH2C( But)=NNH2}2]2+ isolated as the chloride or chloride hexafluorophosphat e salts. The dicationic dichloride reacted with 2 moles of sodium etho xide to give the neutral cis-[Pt{PPhCH2C(But)=NNH}2]. Treatment of [Pd Cl2(NCPh)2] with L2 gave [Pd{PPh2CH2C(But)=NNH2}2]Cl2, which with sodi um ethoxide gave the neutral trans[Pd{PPh2CH2C(But)=NNH}2]. The mixed azine monophosphine PPh2CH2C(But)=N-N=CHPh L3 with [PdCl2(NCPh)2] gave the chelate complex [PdCl2{PPh2CH2C(But)=N-N=CHPh}] and with [PtMe2(c od)] it gave [PtMe2{PPh2CH2C(But)=N-N=CHPh)]. Treatment of [PtCl2(NCMe )2] with 2 equivalents of L3 gave trans-[PtCl2{PPh2CH2C(But)=N-N=CHPh} 2] which on heating gave the dicationic dichloride salt cis-[Pt{PPh2CH 2C(But)=N-N=CHPh}2]Cl2. Successive treatments of this salt with 1 mole of sodium methoxide gave PPh2CH2C(But)=N-N=CHPh}Pt{PPh2CH=C(But)N-N=C HPh}]+ and cis-[Pt{PPh2CH=C(But)N-N=CHPh}2]. Proton, C-13-{H-1}, P-31- {H-1) NMR and infrared data have been obtained. Crystals of cis-[Pt{PP h2CH2C(But)=NNH2}2 are monoclinic, space group P2(1)/c, with a = 1261. 5(2), b = 1794.6(3), c = 1792.0(4) pm and Z = 4; final R = 0.0451 for 4088 observed reflections.