113693-77-9Relevant academic research and scientific papers
A quasi-covalent metal-metal bond in an early-late heterobimetallic Ti-Pt complex stabilized by phosphinoenolate ligands
Braunstein, Pierre,Morise, Xavier,Benard, Marc,Rohmer, Marie-Madeleine,Welter, Richard
, p. 610 - 611 (2007/10/03)
An unusual early-late bimetallic complex with direct metal-metal bonding is obtained from a phosphinoenolate ligand-assisted reaction between Ti(IV) and Pt(0) reagents which occurs by formal insertion of the Pt(0) centre into a Ti(IV)-O bond; X-ray data and EHMO calculations indicate the presence of a quasi-covalent Ti(III)-Pt(I) bond (2.721(2) A).
Reactivity of alpha phosphino enolate complexes of nickel(II) and palladium(II) toward electrophilic metal centers. Synthesis and crystal structures of the bimetallic palladium(II)-gold(I) complex (4a) and of the nickel(II)-cobalt(II) paramagnetic complex (5b) (see abstract)
Andrieu, Jacques,Braunstein, Pierre,Drillon, Marc,Dusausoy, Yves,Ingold, Florent,Rabu, Pierre,Tiripicchio, Antonio,Ugozzoli, Franco
, p. 5986 - 5994 (2008/10/09)
The chemoselective reactivity of metal-coordinated phosphino enolates has been studied by the reactions of cis-[Ni?{R′2PCH?C(?O)R}2] (R = Ph, p-C6H4Me, Me; R′ = Ph, iPr, not all combinations) and [(C N)- Pd{Ph2PCH?C(?O})Ph}] (C N = o-C6H4CH2NMe2, dmba or C10H8N, 8-mq) with different metal electrophiles. In the reaction of cis-[Ni{Ph2PCH?C(?O)Ph}2] (1a) with [PtCl2(COD)] (COD = 1,5-cyclooctadiene), a transmetalation of the P,O ligands was observed, yielding the known complex cis-[Pt{Ph2PCH?C-(?O)Ph}2] (3). However, reaction of cis-[Ni{R′2PCH?C(?O)R}2] with anhydrous CoI2 afforded the heterobinuclear complexes cis-[Ni{R′2PCH?C(?O)R}2]CoI2 (5a, R = Ph, R' = Ph; 5b, R = p-C6H4Me, R' = Ph; 5c, R = Me, R' = Ph; 7, R = Ph, R' = iPr) which contain the phosphino enolate ligand in an unusual chelating-bridging μ-η1(O):η2(P,O) coordination mode in a nonplanar NiO2Co unit. The magnetic properties of these complexes are discussed. The SHOP-type catalyst [Ni(Ph){Ph2PCH?C(?O)Ph}(PPh3)] also behaved as an oxygen-donor metalloligand toward CoI2 to give a paramagnetic Co(II) complex. In contrast, reaction of [(C N)Pd{Ph2PCH?C(?O)Ph}] with [Au(PPh3)]+ occurred with formation of [(dmba)-Pd{Ph2PCH(AuPPh3)C(O)Ph}](BF4) (4a) in which a Cenolate-Au bond has been formed while the P,O chelate has remained coordinated to palladium. This reaction generates a new stereogenic center, as also evidenced by 1H NMR spectroscopy. The solid state structures of complexes 4a·1/2C7H8 and 5b·CH2Cl2 have been determined by single-crystal X-ray diffraction: 4a·1/2C7H8 crystallizes in the triclinic space group P1? with Z = 2 in a unit cell of dimensions a = 16.778(4) A?, b= 14.269(5) A?, c = 10.838(6) A?, α = 79.27(4)°, β= 71.59(3)°, and γ = 72.68(2)°; 5·CH2Cl2 crystallizes in the monoclinic space group P21ln with Z = 4 in a unit cell of dimensions a = 12.940(1) A?, b = 18.329(2) A?, c = 18.495(2) A?, and β= 91.627(8)°. The structures have been solved from diffractometer data by direct and Fourier methods and refined by full-matrix least-squares methods on the basis of 7240 (4a·1/2C7H8) and 3644 (5b·CH2Cl2) observed reflections to R and Rw values of 0.0363 and 0.0406 (4a·1/ 2C7H8) and 0.040 and 0.038 (5b·CH2Cl2), respectively.
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.
