113693-91-7Relevant academic research and scientific papers
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.
