28069-69-4Relevant articles and documents
Synthesis and reactivity of silyl iron, cobalt, and nickel complexes bearing a [PSiP]-pincer ligand via Si-H bond activation
Wu, Siquan,Li, Xiaoyan,Xiong, Zichang,Xu, Wengang,Lu, Yunqiang,Sun, Hongjian
, p. 3227 - 3237 (2013/07/19)
The synthesis and characterization of a series of Ni, Co, and Fe complexes bearing a tridentate bis(phosphino)silyl ligand (κ3-(2-Ph 2PC6H4)2SiMeH, [PSiP]-H, 1) are reported. 1 reacted with Ni(PMe3)4 to afford the mononuclear nickel(0) complex [η2(Si-H)-PSiP]Ni(PMe3) (2). The halogeno nickel complexes [PSiP]Ni(X)(PMe3) (X = Cl (3), Br (4), I (5)) were synthesized in the reactions of 2 with Me3SiCl or MeHSiCl2, EtBr, and MeI. Complex 2 underwent ligand substitution of PMe3 by CO to give [η2(Si-H)-PSiP]Ni(CO) (6). Complex 3 reacted with NaOMe to deliver [PSiP]Ni(OMe)(PMe3) (7) through anionic ligand substitution, while the neutral ligand replacement of PMe 3 by CO in 3 afforded the rare hexacoordinate 20-electron nickel(II) complex [PSiP]Ni(Cl)(CO)2 (8). Unexpectedly, reaction of 1 with NiMe2(PMe3)3 produced the tetracoordinate nickel(0) complex [Me2PSiP]2Ni (9). The complex [Me 2PSiP]Ni(CO)2 (10) was acquired from 9 after the substitution of one [PSiP] ligand by two carbonyl ligands. 1 reacted with Co(PMe3)4 or CoCl(PMe3)3 to afford the hydrido cobalt(II) complex [PSiP]CoH(PMe3) (11) or hydrido cobalt(III) complex [PSiP]Co(H)(Cl)(PMe3) (13). Complex 12, [PSiP]Co(H)(I)(PMe3), could be obtained from the reaction of MeI with 11 or 13. Treatment of 13 with 1 equiv of MeLi or n-BuMgBr in THF resulted in the clean formation of cobalt(I) complex [PSiP]Co(PMe3)2 (14) via reductive elimination. The simple anhydrous inorganic salt NiCl 2 or CoCl2 could also react with 1 in the presence of PMe3 to form the corresponding silyl complexes 3 and [PSiP]Co(Cl)(PMe3) (15) via Si-H bond cleavage. 1 reacted with Fe(PMe3)4 to form the hexacoordinate octahedral hydrido iron(II) complex [PSiP]Fe(H)(PMe3)2 (16). The molecular structures of complexes 2-5, 10, 12, 13, 15, and 16 were determined by X-ray single crystal diffraction. 16 has excellent catalytic reactivity for the reduction of aldehydes and ketones.
Syntheses and properties of molecular nickel(II) hydride, methyl, and nickel(I) complexes supported by trimethylphosphane and (2-diphenylphosphanyl)thiophenolato and -naphtholato ligands
Kraikivskii, Peter B.,Frey, Markus,Bennour, Hamdi A.,Gembus, Armin,Hauptmann, Ralf,Svoboda, Ingrid,Fuess, Hartmut,Saraev, Vitaly V.,Klein, Hans-Friedrich
, p. 1869 - 1876 (2009/08/14)
(2-Diphenylphosphanyl)thiophenol (P^pSH) or (3-diphenylphosphanyl)-2-thionaphthol (P^nSH) react with Ni(PMe3)4 to form NiH(P^pS)(PMe3)2 (1) or NiH(P^nS)(PMe3)2 (2). 1,3-Bis(diphenylphosphanyl)propane (P^P) replaces the monodentate phosphane ligands to give NiH(P^pS)(P^P) (3). NiMe(OMe)(PMe3) or NiMe2(PMe3)3 react with P^pSH to form NiMe(P^pS)(PMe3) (4) and NiMe(P^pS)(PMe3)2 (5), respectively, and P^nSH affords NiMe(P^nS)(PMe3)2 (6), NiMe(P^nS)(PMe3) (7). Dissociation of PMe3 ligands induces transformation of 1 to Ni(P^pS)(PMe3)2 (8) and Ni(P^pS)2. Crystal and molecular structures are given for 1, 5-8, and dynamic solution spectra (NMR, EPR) are discussed.
Insertion of alkynes into Ni-H bonds: Synthesis of novel vinyl nickel(II) and dinuclear vinyl nickel(II) complexes containing a [P, S]-ligand
She, Lei,Li, Xiaoyan,Sun, Hongjian,Ding, Jun,Frey, Markus,Klein, Hans-Friedrich
, p. 566 - 570 (2008/10/09)
Reactions of alkynes with nickel hydride complexes bearing a [P, S]-ligand and supported by trimethylphosphine were investigated. Tetracoordinate vinyl nickel(II) complexes 3, 5, and 6 with square-monoinsertionplanar geometry were obtained by reacting phenylacetylene, trimethylsilylacetylene, and 1-hexyne with the hydrido nickel complex 1. Reaction of 1,4-bis(trimethylsilylethynyl)benzene with complex 1 proceeds as a monoinsertion and afforded complex 7, while reaction of 1,4-bis(ethynyl)benzene with 1 leads to the dinuclear vinyl nickel(II) complex 8.
Insertion of Alkynes into Organonickel Functions as a Synthesis of Vinylnickel Compounds
Klein, Hans-Friedrich,Reitzel, Lutz
, p. 1115 - 1118 (2007/10/02)
The diamagnetic vinylnickel compounds trans-Ni(CR1=CR2R3)Cl(PMe3)2 (1a: R1 = R2 = C6H5, R3 = CH3; 2a: R1= C6H5, R2 = R3 = CH3; 3a: R1 = R2 = CH3, R3 = C6H5; 4a: R1 = R2 = R3 = C6H5) and Ni(CR1=CR2R3)(acac)(PMe3) (5: R1 = R2 = C6H5, R3 = CH3) are formed by insertion of diphenylethyne and 1-phenylpropyne into methyl- or phenylnickel moieties as Z isomers, that are thermally equilibrated with their E isomers. 1-Phenylethyne and 1-phenylpropyne selectively produce (1-phenylvinyl)nickel compounds.Exchange of halide gives bromides 1b, 2b, 4b and iodides 1c, 2c, 4c, and a cyanide 1d.Action of LiR (R = Me, CCCMe3) on 1a followed by reductive elimination yields olefins RR1C=CR2R3 while mineral acids or iodine cleave the Ni-C bonds of 1a to give the corresponding olefins (R = H, I).A high-yield synthesis of chloro(phenyl)bis(trimethylphosphane)nickel is also described.
Oxidative coupling of phosphinomethanides at a metal centre: P-P vs. C-C bond formation and the molecular structure of the novel bis-ylide (Me 3Si)2C=PMe2-PMe2=C(SiMe 3)2
Karsch, Hans H.,Deubelly, Brigitte,Mueller, Gerhard
, p. 517 - 518 (2007/10/02)
Metal induced coupling of [CH2PMe2]- leads to Me2PCH2CH2PMe2, whereas coupling of [C(X)(SiMe3)(PMe2)]- (X=SiMe3 or PMe2) results in P-P bond formation affording [(X)(SiMe 3)C=PMe2-]2, with a central P-P bond of length 2.278(1) A.
FUNKTIONELLE TRIMETHYLPHOSPHANDERIVATE. XIX. PHOSPHINOMETHYLSUBSTITUIERTE ZIRCONIUMVERBINDUNGEN ALS NUCLEOPHILE: SYNTHESE, REAKTION MIT CO UND MOLEKUELSTRUKTUR VON 2Ni
Karsch, Hans H.,Mueller, Gerhard,Krueger, Carl
, p. 195 - 212 (2007/10/02)
The organozirconium-substituted phosphines Cp2Zr(X)CH2PMe2 (Cp = η5-C5H5; X = Cl, CH2PMe2) have been prepared from Cp2ZrCl2 and LiCH2PMe2.In these compounds, the phosphinomethyl group acts as a monohapto (η1-) ligand.On reaction with CO, the bis(phosphinomethyl)zirconium complex forms a red complex, which by means of NMR spectroscopy is shown to contain a novel zircona heterocycle.With Ni(COD)2, Cp2Zr(CH2PMe2)2 forms the 2:1 complex 2Ni.Crystals (from tetrahydrofuran) are triclinic, space group P, with parameters a 13.433(5), b 18.062(3), c 19.505(2) Angstroem, α 64.35(2), β 76.82(1), γ 71.28(2) deg, V 4018.12 Angstroem3, dx 1.445 g cm-3 for Z = 4, μ(Mo-Kα) 11.5 cm-1, T 21 deg C.Refinement of 743 parameters on 8826 reflections converged at R = 0.055.The molecular structure consists of monomeric units with two bidentate Cp2Zr(CH2PMe2)2 molecules acting as chelating ligands to a tetrahedral Ni0 centre.The six-membered Zr(CH2PMe2)2Ni rings adopt a chair conformation.Steric strain by interaction of the axial cyclopentadienyl and methyl ligands at Zr and P, respectively, causes these rings to be considerably flattened.
