46225-54-1

Upstream product

• 12775-96-1 copper 
• 829-85-6 diphenylphosphane 
• 60842-00-4 copper(I) tert-butoxide 

Downstream Products

• 875556-80-2 Cu⁽¹⁺⁾*P(C₆H₅)2^(1-)*C₁₄H₁₂N₂ = [Cu(P(C₆H₅)2)(C₁₄H₁₂N₂)] 

Relevant academic research and scientific papers

The Direct Electrochemical Synthesis of Metal-Diphenylphosphido Complexes, and the Crystal Structure of Cu4(μ-PPh2)4(Ph2PCH2PPh2)2

The electrochemical oxidation of metal anodes in an acetonitrile solution of Ph2PH yields M(PPh2) (M=Cu, Ag, Au) or M(PPh2)2 (M=Co, Zn, Cd); with a solution of Ph2PH and bis(diphenylphosphino)methane (dppm), this method gives Cu4(PPh2)4(dppm)2 whose structure is found to be very similar to that of Cu4(SC5H11)4(dppm)2.

Phosphinohydrazines and phosphinohydrazides M(-N(R)-N(R) -PPh2)n of some transition and main group metals: Synthesis and characterization. Rearrangement of Ph2 P-NR-NR- ligands into aminoiminophosphorane, RN=PPh2-NR-, and related chemistry

The reactions of phosphinohydrazines ArNH-N(Ar)-PPh2 {Ar = Ph (2a), p-But-C6H4- (2b)} with metal silylamides M[N(SiMe3)2]n, {M = Fe(II), Fe(III), Co(II), Ni(I), Cu(I)} or the reactions of lithium salts ArN(Li)-N(Ar)-PPh2 with metal halides (GeCl2, ZnCl2, FeBr2, CoCl2, NiBr2, CrCl3, MnCl2) are strongly dependent on nature of a metal and its ligand environment. Early transition metals or non-transition metals form stable phosphinohydrazides M[N(Ar)N(Ar)PPh2]n {M = Li, Zn, Ge(II), Mn(II), Cr(III), Fe(II)}. Starting ligand 2a and germylene Ge(NPhNPhPPh2)2 (7) were characterized by X-ray analysis. Germanium is coordinated additionally with a phosphorus atom of one of the diphenylphosphine groups.The distance Ge?P was found to be 2.563(1) ?. This coordination leads to an appreciable increase in a pyramidal geometry of nitrogen atoms relatively to a non-coordinated fragment.Late transition metals (Co, Ni, Cu) and metals with enhanced oxidation state (Fe3+) cause transformation of a phosphinohydrazide ligand.For Co(II), Ni(II), Fe(III) this leads quantitatively to aminoiminophosphoranates M(NAr-PPh2NAr) n. Complex Co[N(C6H4But) -PPh2 = N-C6H4But] 2 (11) was characterized by X-ray analysis. Nickel(I) silylamide, (Ph3P)2NiN(SiMe3) 2, being reacted with 2a yields azobenzene complex, (Ph3P)2Ni(PhN = NPh), while copper(I) silylamide originally forms (PhNH-NPh-PPh2)2 CuN(SiMe3)2 (18). Heating of the latter in toluene solution yields insoluble copper(I) diphenylphosphide, azobenzene, 2a and hexamethyldisilazane. The reaction of hydrazobenzene with Ph2PCl (1:1) in methylene chloride for three days gives aminoiminophosphorane dihydrochloride[PhNH-PPh2NPh]· 2HCl (3) in quantitative yield.

Direct Electrochemical Synthesis and Crystallographic Characterization of Metal Diphenylphosphido and Diphenylthiophosphinato Compounds, and some Derivatives

The electrochemical oxidation of a number of metals in acetonitrile solutions of PPh2H gives rise to M(PPh2)n compounds (M = Co, Zn or Cd, n = 2; M = Cu, Ag or Au, n = 1).With anodic nickel the product is Ni(PPh2).PPh2H.In the presence of elemental sulphur such oxidation reactions yield (M = Co, Zn or Cd).The electrochemical processes involved have been identified.The crystal structure of the addition compound .4MeCN 1 has been determined by X-ray crystallography, which reveals a Cu4P4 ring, capped by Cu2PCP'2 rings.Crystal parameters: triclinic, space group P1, a = 14.719(4), b = 13.649(5). c= 17.112(5) Angstroem, α = 112.40(3), β = 106.22(2), γ = 115.39(2) deg and Z = 1; R = 0.0632 for 3622 observed reflections = 3?(l)>.The compound Ni)PPh2).PPh2H is oxidized by elemental oxygen, sulphur or selenium to give (E = O, S or Se), and also reacts with PhNCS to yield 2>. 2.Crystal parameters: triclinic, space group P1, a= 8.950(6), b = 9.745(4), c = 10.366(7) Angstroem, α = 112,28(4), β = 99.09(5), γ = 90.88(4) deg, and Z = 1.Disorder prevented this structure from being refined beyond R = 0.1612, but the essential features of the square-planar NiS2P2 core were identified.The crystal parameters of 3 are monoclinic, space group P2,/c, a = 12.420(5), b = 9.737(7), c = 20.729(16) Angstroem, β = 100.29(5) deg, and Z = 2.The nickel atom is co-ordinated by two monodentate Ph2PO(O)- ligands and two monodentate Ph2P(O)OH ligands which are hydrogen-bonded to their anionic analogues, and by two MeCN molecules, to give a NiO2O'2N2 core.

Alcohol elimination chemistry of (CuOtBu)4

The Bronsted basicity of (CuOtBu)4 was tested against a range of weak acids. With (Ph2P)2CH2, tBuOH is eliminated, with production of the cage molecule Cu3(Ph2PCHPPh2)3, which was characterized by 1H and 31P NMR spectra. With Ph2PH, tBuOH is eliminated to precipitate (CuPPh2)x, which can be dissolved with L = Ph2PH or PPh3 to give [(Ph2PH)CuPPh2]x and monomeric Ph3PCuPPh2. With Ph2P(CH2)2PPh2, deprotonation of a CH2 group is followed by P-C bond cleavage to give LCuPPh2, where L may be either Ph2PCH=CH2 or excess phosphine chelate. The vinyl group in this phosphine (either generated from Ph2P(CH2)2PPh2 or as added Ph2PCHCH2) is catalytically hydrogenated in this reaction system (100 atm H2, 25°C). (CuOtBu)4 reacts with PPh3 to yield the dimer (Ph3PCuOtBu)2, shown by X-ray diffraction to be a gull-winged dimer. This molecule does not dissolve intact in toluene, but shows partial phosphine ligand redistribution to (CuOtBu)4 and a more phosphine-rich species. Crystallographic data (-165°C): a = 10.327 (4) A?, c = 36.669 (20) A? with Z = 4 in space group P41212.