177490-53-8Relevant academic research and scientific papers
Synthesis and characterisation of E,O-mixed donor (E = P, S or Se) ligand complexes of palladium(II) and platinum(II)
Smith, Martin B.,Slawin, Alexandra M.Z.
, p. 172 - 179 (2008/10/08)
New palladium(II) and platinum(II) complexes with the hybrid ligands Ph2PNHP(O)Ph2, [Ph2PNP(O)Ph2]- or [Ph2P(E)NP(O)Ph2]- (E = S or Se) have been prepared and characterised. Hence reaction of the cyclometallated dimers [{Pd(μ-Cl)(C ~ N)}2] [C ~ N=C12H9N2 or C13H8N] with Ph2PNHP(O)Ph2 gave the mononuclear compounds [PdCl(C ~ N){Ph2PNHP(O)Ph2-P}]. Chloride abstraction, or amine deprotonation, afforded [Pd(C ~ N){Ph2PNHP(O)Ph2-P,O}][BF4] or [Pd(C ~ N){Ph2PNP(O)Ph2-P,O}] bearing a neutral or anionic P,O-chelating ligand, respectively. Reaction of [{Pd(μ- Cl)(C9H12N)}2] with Ph2PNHP(O)Ph2 in CDCl3 solution gave the known, rather unstable compound, [PdCl(C9H12N)-{Ph2PNHP(O)Ph2-P}]. Spectroscopic and analytical evidence presented here suggest that [PdCl(C9H12N){Ph2PNHP(O)Ph2-P}] undergoes amine deprotonation/Pd-C bond rupture to give an isomeric compound, tentatively assigned as [PdCl{Ph2PNP(O)Ph2-P,O}(NMe2CH2Ph)]. Bridge cleavage of [{Pd(μ-Cl)(C12H9N2)}2] with the unsymmetrical anions [Ph2P(E)NP(O)Ph2]- (E = S or Se) gave the square-planar complexes [Pd(C12H9N2){Ph2P(E)NP(O)Ph2-E,O}] exclusively as one isomer (E trans to N). In a similar manner the new metal(II) compounds [PtCl{Ph2P(E)NP(O)Ph2-E,O}(PMe2Ph)] (E trans to Cl) and [Pd(C9H15O)-{Ph2P(E)NP(O)Ph2-E,O}] (E trans to olefin double bond) were synthesised. All compounds were characterised by a combination of multinuclear NMR [1H, 31P{1H}, 195Pt{1H}], IR spectroscopy and elemental analyses. Furthermore, the X-ray structures of [Pd(C12H12N){Ph2PNHP(O)Ph2-P,O}][BF4] and [Pd(C12H12N){Ph2PNP(O)Ph2-P,O}] are reported and reveal, upon amine deprotonation, π-delocalisation within the P-N-P-O backbone of the anionic P,O-chelating ligand. (C) 2000 Elsevier Science S.A.
Palladium(II) and Platinum(II) Complexes of the Heterodifunctional Ligand Ph2PNHP(O)Ph2
Bhattacharyya, Pravat,Slawin, Alexandra M. Z.,Smith, Martin B.,Woollins, J. Derek
, p. 3675 - 3682 (2008/10/09)
The noncomplexed ligand Ph2PNHP(O)Ph2 (HL) has been prepared, for the first time, from Ph2PNHPPh2 (dppa) and H2O2 in moderate yield. On further treatment with H2O2 the
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.
