TERDENTATE (P-N-O) COMPLEXES FORMED FROM Z,E-PPH(2)CH(2)C(BU(T))=N-N=CH(C6H4OH-2) OR Z,E-PPH(2)CH(2)C(BU(T))=N-N=CH[C6H2(OH-2)(OME)(2)-4,6] AND NICKEL, PALLADIUM, PLATINUM, RHODIUM OR IRIDIUM

Condensation of Z-PPh(2)C(2)C(Bu(t))=NNH2 with salicylaldehyde or 4,6-dimethoxysalicylaldehyde gave the azine phosphines Z,E-PPh(2)CH(2)C(Bu(t))=N-N-CH(C6H4OH-2) 1a or Z,E-PPh(2)CH(2)C(Bu(t))=N-N=CH[C6H2(OH-2)(OMe)(2)-4,6] 1b, respectively. Treatment of 1a with [PdCl2(cod)] (cod = cyclo-octa-1,5-diene) gave the bidentate chelate complex [PdCl2{PPh(2)CH(2)C(Bu(t))=N-N=CH(C6H4OH-2)}] 3. The phosphine 1 a reacts with Na2PdCl4 in the presence of NaO(2)CMe to give the terdentate chelate complex [PdCl{PPh(2)CH(2)C(Bu(t))=N-N=CH(C6H4O)}] 49. Treatment of the latter with Nal or MgMel gave the corresponding iodopalladium(II) complex 4b or the methylpalladium(II) complex 4c. respectively. The analogous methylplatinum(II) complex [PtMe{PPh(2)CH(2)C(Bu(t))=N-N=CH(C6H4O)}] 4d was prepared by treating [PtMe(2)(cod)] with 1a. Fluxional nickel(II) complexes of type [NiX{PPh(2)CH(2)C(Bu(t))=N-N=CH(C6H4O)}] (X = Cl 4e or Br 4f) were also prepared from NiX(2).nH(2)O. When Ni(O(2)CMe)(2).4H(2)O was treated with two mot equivalents of 1a a paramagnetic octahedral nickel(II) complex [Ni{PPh(2)CH(2)C(Bu(t))=N-N=CH(C6H4O)}(2)] 5 was formed. Treatment of [PtCl2(cod)] with two mol equivalents of 1a in the presence-of NaO(2)CMe gave a monocationic platinum(II) chloride salt, which with NH4PF6 gave the PF6 salt. Treatment of 1b with [IrCl(CO)(2)(MeC(6)H(4)NH(2)-p)] or 0.5 equivalents of [Rh2Cl2(CO)(4)] in the presence of NEt(3) gave the square-planar complexes [M(CO){PPh(2)CH(2)C(Bu(t))=N-N=CH[C6H2O(OMe)(2)-4,6]}] (M = Ir 7a or Rh 7b). The carbonyliridium(I) complex 7a underwent oxidative-addition reactions with Mol, allyl chloride, acetyl chloride or propargyl chloride to give the halogenocarbonyliridium(III) complexes [IrX(R)(CO){PPh(2)CH(2)C(Bu(t))=N-N=CH[C6H2O(OMe)2-4,6]}] 8a-8d respectively. In contrast, the reaction of the carbonylrhodium(I) complex 7b with allyl chloride gave the pi n-allylrhodium(III) complex [RhCl(eta(3)C(3)H(5){PPh(2)CH(2)C(Bu(t))=N-N=CH[C6H2O(OMe)(2)-4,6]}] 9. Proton, P-31-{H-1} and some C-13-{H-1} NMR data have been attained.