名称:
Terdentate (P,N,N) complexes of a new pyridyl azine phosphine Z,E-PPh2CH2(But)CN–NC(Me)C5H4N and its deprotonated derivative (an azo phosphine) with transition metals
摘要:
tert-Butyl diphenylphosphinomethyl ketone hydrazone, Z-PPh2CH2C(Bu(t))=NNH2 condensed with 2-acetylpyridine to give Z,E-PPh2CH2(Bu(t))C=N-N=C(Me)C5H4N Ia, which reacts with [M(CO)4(nbd)] (nbd = norbornadiene) to give highly coloured tricarbonyl complexes [M(CO)3{PPh2CH2C(Bu(t))=N-N=C(Me)C5H4N}] (M = Mo 1a, W 1b or Cr 1c). Under mild conditions, Ia reacted with [PtMe2(cod)] (cod = cycloocta-1,5-diene) to give the dimethylplatinum(II) complex [PtMe2{PPh2CH2C(Bu(t))=N-N=C(Me)C5H4N}] 2 containing the bidentate azine phosphine ligand. Complex 2 reacted with Mel to give the fac-trimethylplatinum(IV) iodide salt [PtMe3{PPh2CH2C(Bu(t))=N-N=C(Me)C5H4N}]I 3 in which the phosphine is terdentate. Under slightly acidic conditions, Ia reacted with [PtMe2(cod)] to give a yellow methylplatinum(II) cation isolated as the PF6 salt, [PtMe{PPh2CH2C(Bu(t))=N-N=C(Me)C5H4N}]PF6 4a. Deprotonation of this cation with NaOMe gave the deep blue neutral methylplatinum(II) complex [PtMe{PPh2CH=C(Bu(t))-N=N-C(Me)=C5H4N}] 5a, containing a terdentate azo phosphine ligand. Treatment of [PtCl2(cod)] with Ia gave the yellow chloride salt [PtCl{PPh2CH2C(Bu(t))=N-N=C(Me)C5H4N}]Cl 4b, which with NH4PF6 gives the corresponding PF6 salt 4c. Sodium methoxide immediately deprotonates 4b to give the intensely deep blue neutral chloroplatinum(II) complex [PtCl{PPh2CH=C(Bu(t))-N=N-C(Me)=C5H4N}] 5b. Treatment of [PdCl2(NCPh)2] with Ia gave the yellow chloropalladium(II) chloride salt [PdCl{PPh2CH2C(Bu(t))=N-N=C(Me)C5H4N}]Cl 4d, which on deprotonation with NEt3, gives the deep purple, neutral chloropalladium(II) complex 5c. Infrared, P-31-{H-1}, H-1, some C-13-{H-1} NMR and UV/VIS data are given.