179076-11-0Relevant academic research and scientific papers
A Mild One-Pot Reduction of Phosphine(V) Oxides Affording Phosphines(III) and Their Metal Catalysts
Kapu?niak, ?ukasz,Plessow, Philipp N.,Trzybiński, Damian,Wo?niak, Krzysztof,Hofmann, Peter,Jolly, Phillip Iain
, p. 693 - 701 (2021/04/06)
The metal-free reduction of a range of phosphine(V) oxides employing oxalyl chloride as an activating agent and hexachlorodisilane as reducing reagent has been achieved under mild reaction conditions. The method was successfully applied to the reduction of industrial waste byproduct triphenylphosphine(V) oxide, closing the phosphorus cycle to cleanly regenerate triphenylphosphine(III). Mechanistic studies and quantum chemical calculations support the attack of the dissociated chloride anion of intermediated phosphonium salt at the silicon of the disilane as the rate-limiting step for deprotection. The exquisite purity of the resultant phosphine(III) ligands after the simple removal of volatiles under reduced pressure circumvents laborious purification prior to metalation and has permitted the facile formation of important transition metal catalysts.
Mechanistic Studies on Halo-Ligand Substitution of Five-Coordinate Trigonal-Bipyramidal Palladium(II) Complexes of Tris(2-(diphenylphosphino)ethyl)phosphine with Trimethyl Phosphite in Chloroform at Various Temperatures and Pressures
Aizawa, Sen-Ichi,Iida, Takashi,Funahashi, Shigenobu
, p. 5163 - 5167 (2008/10/09)
Five-coordinate trigonal-bipyramidal palladium(II) complexes [Pd(pp3)X]X (pp3 = tris(2-(diphenylphosphino)-ethyl)phosphine, X-- = Cl-, Br-, I-) have been synthesized, and their structures i
Co-ordination Chemistry of Higher Oxidation States. Part 4.1 Palladium(IV) Complexes of Nitrogen, Phosphorus, and Arsenic Donor Ligands. Crystal and Molecular Structures of and 2Cl2>2
Gray, Leslie R.,Gulliver, David J.,Levason, William,Webster, Michael
, p. 133 - 142 (2007/10/02)
Octahedral palladium(IV) complexes have been prepared by chlorine oxidation of .The corresponding have been obtained, but the (L-L = N-donors above, Ph2PCH2CH2PPh2 and Ph2AsCH2CH2AsPh2) were not oxidised by bromine.The complexes (X = Cl or Br) reductively eliminate X2 on gentle heating.Chlorine oxidation of Pd(L-L)2Cl2 gave Pd(L-L)2Cl4 for L-L = Me2PCH2CH2PMe2 and o-C6H4(PMe2)2, but gave for L-L = Ph2PCH2CH2PPh2, Ph2AsCH2CH2AsPh2, and o-C6H4(AsMe2)2.The complexes trans-2 were obtained by HNO3-HX oxidation of Pd(L-L)2X2 followed by addition of HClO4.Infrared, electronic, and 1H n.m.r. spectra are reported for the complexes.Attempts to prepare PdIV complexes with multidentate phosphines and arsines are described.The structures of the title compounds have been established by single-crystal X-ray studies.The complex is monoclinic, space group Pn, a = 12.241(5), b = 6.720(2), c = 8.120(9) Angstroem, β = 104.37(5) deg, and Z = 2. 1 383 Observed reflections refined R to 0.023.The crystal contains discrete octahedral molecules .The complex 2Cl2>2 is triclinic, space group P1, a = 7.903(3), b = 10.670(3), c = 10.141(2) Angstroem, α = 110.50(2), β = 91.75(3), γ = 107.31(3) deg, and Z = 1. 1 680 Observed reflections refined R to 0.039.The crystal contains trans octahedral cations and perchlorate ions .
