175657-34-8Relevant academic research and scientific papers
Ph2PNHP(O)Ph2, a versatile new ligand: Syntheses of monodentate and chelating complexes and a novel Pd2P4N2O2 metallocycle
Smith, Martin B.,Slawin, Alexandra M. Z.,Woollins, J. Derek
, p. 1579 - 1583 (1996)
Oxidation of Ph2PNHPPh2 gave Ph2PNHP(O)Ph2 (1), which reacted with (C3H5)PdCl2Pd(C3H5) to form (C3H5)PdCl(Ph2PNHP(O)Ph2) (2). Treatment of 2 with Ag[BF4] or ButOK yielded the almost planar five-membered PdP2NO metallocycle [(C3H5)Pd(Ph2PNHP(O)Ph2)]BF 4 (3) or the 'chair'-like 10-membered metallocycle [(C3H5)Pd(Ph2PNP(O)Ph2) 2Pd(C3H5)] (4) respectively.
Late transition-metal complexes with the heterofunctional phosphine Ph2PNHP(O)Ph2
Slawin, Alexandra M. Z.,Smith, Martin B.,Woollins, J. Derek
, p. 1283 - 1293 (2007/10/03)
The complexes [MCl(cod)(HL)] (M = Rh or Ir), [PdCl(η3-C3H5)(HL)], [PdCl(L-L)(HL)], trans-[RhCl(CO)(HL)2] and [AuCl(HL)] have been synthesised by reaction of either [{M(μ-Cl)(cod)}2] (M = Rh or Ir; cod = cycloocta-1,5-diene), [{Pd(μ-Cl)(η3-C3H5)}2], [{Pd(μ-Cl)(L-L)}2] (L-L = C12H12N, C10H8N or C9H12N), [{Rh(μ-Cl)(CO)2}2] or [AuCl(tht)] (tht = tetrahydrothiophene) with Ph2PNHP(O)Ph2 (HL). In all these complexes the ligand is monodentate P-bound. Chloride abstraction from [PdCl(C12H12N)(HL)] or [PdCl(η3-C3H5)(HL)], using Ag[BF4], gave the cationic compounds [Pd(C12H12N)(HL)][BF4] or [Pd(η3-C3H5)(HL)][BF4] in which the ligand HL is P,O-chelated. Removal of the amine proton in metal complexes of HL (monodentate P-bound) with KOBut afforded a new class of neutral metallacycles incorporating either an MP2NO or M2P4N2O2 framework based on the [Ph2PNP(O)Ph2]- (L-) ligand. Reaction of [{Pd(μ-Cl)-(C9H12N)}2] with 4 equivalents of HL in methanol at ambient temperature yielded the neutral palladium(II) complex [PdCl{Ph2PNP(O)Ph2-P,O}(Ph2POMe)] in which one HL ligand has undergone P-N bond scission. The reaction of the iridacycle [Ir(COd){Ph2PNP(O)Ph2-P,O}] with MeI was shown to proceed with cis addition affording the iridium(III) metallacycle [IrI(Me)(cod){Ph2PNP(O)Ph2-P,O}]. All compounds described have been characterised by a combination of 31P-{1H} NMR spectroscopy, microanalysis and in some cases by 1H NMR and IR spectroscopy. The molecular structures of four complexes have been determined by single-crystal X-ray diffraction. The metallacycles show π-electron delocalisation in the P-N-P-O fragment.
