97954-27-3Relevant articles and documents
Complexes of Functional Phosphines. Part 11. β-Ketophosphine Complexes of Nickel, Palladium, and Platinum. Crystal Structures of trans-
Braunstein, Pierre,Matt, Dominique,Nobel, Dominique,Balegroune, Fadila,Bouaoud, Salah-Eddine,et al.
, p. 353 - 362 (2007/10/02)
The synthesis and spectroscopic properties (1H and 31P n.m.r., i.r.) of complexes containing the β-ketophosphine Ph2PCH2C(O)Ph (HL) are described.In , (4), (5), and 2> (6), HL behaves as a P-bonded monodentate ligand whereas in the cationic complexes 2 and 2>2 it acts as a P, O chelate.The crystal structures of (1) and (3) have been determined using single-crystal X-ray diffraction methods.Compound (1) crystallises in space group P21/n, with a=10.079(3), b=11.510(3), c=15.411(3) Angstroem, β=93.42(2) deg, and Z=2.Compoumd (3) crystallises in space group P21/c, with a=9.283(1), b=10.261(1), c=19.318(1) Angstroem, β=96.20(1) deg, and Z=2.The structures have been refined to R 0.050 (R' 0.060) for (1) and to R 0.032 (R' 0.041) for (3).The geometries of these complexes are essentially identical although the ν(CO) frequencies of these complexes are significantly different -1 for (1) and 1 620 cm-1 for (3)>; the nickel atom occupies a centre of symmetry and has thus a square-planar environment.Although the ketone group is bent towards the nickel atom, no significant Ni-O bonding interaction occurs, as deduced from the Ni-O distances .In refluxing toluene (1), (4), or (5) lead to the phosphine-phosphinite complexes cis- (M=Ni, Pd, or Pt).Treatment of (1), (4), or (5) with base gives the enolato-complexes cis- (M=Ni, Pd, or Pt).Reaction of (6) with NaH affords the binuclear complex .The latter reacts with PPh3 to give cis-, and with Ph2PCH2CH2PPh2-TIPF6 to give .The P-O coupling products (R=Cl or Ph) are obtained by reaction of the complex with PCl3 and PPhCl2 respectively, and shown to have a five-co-ordinate structure.The square-planar P,P,P complex results from reaction of with TIPF6.
ORGANONICKEL CHEMISTRY. I. THE CRYSTAL AND MOLECULAR STRUCTURES OF Ph3PNi(Ph)(Ph2PCHCOPh) AND cis-Ni(Ph2PCHCOPh)2*0.5C7H8
Qichen, Huang,Minzhi, Xu,Yanlong, Qian,Weihua, Xu,Meicheng, Shao,Youqi, Tang
, p. 419 - 426 (2007/10/02)
Reaction of Ni(Cod)2, Ph3P and Ph3PCHCOPh in toluene affords Ph3PNi(Ph)(Ph2PCHCOPh) (I), but with Ph3As instead of Ph3P, it affords cis-Ni(Ph2PCHOPh)2*0.5tol (II).The crystal and molecular structures have been studied by X-ray diffraction.The crystals of I, are monoclinic, space group Cc, with a 13.549(7), b 13.775(3), c 19.763(6) Angstroem, β 102.34(3) deg, V 3603(2) Angstroem3, Z = 4.The final R factor is 0.070 for 1392 observed reflections.The crystals of II are monoclinic, space group C2/c, with a 27.425(7), b 11.113(2), c 24.534(7) Angstroem; β 108.27(2) deg, V 7100(3) Angstroem3, Z = 8.The final R factor is 0.083 for 1409 observed reflections.The coordinations of the nickel atoms in both structures are square planar, and the bond lengths and bond angles in the five-membered ring indicate a delocalized system.
