15376-83-7Relevant articles and documents
Monometallic Ni0 and Heterobimetallic Ni0/AuI Complexes of Tripodal Phosphine Ligands: Characterization in Solution and in the Solid State and Catalysis
Cluff, Kyle J.,Bhuvanesh, Nattamai,Blümel, Janet
, p. 10138 - 10148 (2015/07/07)
The tridentate chelate nickel complexes [(CO)Ni{(PPh2CH2)3CMe}] (2), [(CO)Ni{(PPh2CH2CH2)3SiMe}] (6), and [Ph3PNi{(PPh2CH2CH2)3SiMe}] (7), as well as the bidentate complex [(CO)2Ni{(PPh2CH2)2CMeCH2PPh2}] (3) and the heterobimetallic complex [(CO)2Ni{(PPh2CH2)2CMeCH2Ph2PAuCl}] (4), have been synthesized and fully characterized in solution. All 1H and 13C NMR signal assignments are based on 2D-NMR methods. Single crystal X-ray structures have been obtained for all complexes. Their 31P CP/MAS (cross polarization with magic angle spinning) NMR spectra have been recorded and the isotropic lines identified. The signals were assigned with the help of their chemical shift anisotropy (CSA) data. All complexes have been tested regarding their catalytic activity for the cyclotrimerization of phenylacetylene. Whereas complexes 2-4 display low catalytic activity, complex 7 leads to quantitative conversion of the substrate within four hours and is highly selective throughout the catalytic reaction.
Oxidative Addition of Esters of Formic Acid and β-Lactones to Ni(0)-Complexes Involving Cleavage of the C-O Bond
Yamamoto, Takakazu,Ishizu, Junichi,Yamamoto, Akio
, p. 623 - 624 (2007/10/02)
Reactions of esters of formic acid, HCOOR (R = C2H5, CH2C6H5), with Ni(0)-complexes (mixtures of bis(1,5-cyclooctadiene)nickel (Ni(cod)2) and tertiary phosphines (PR'3)), lead to decarbonylation of HCOOR to afford (Ni(CO)n(PR''3)4-n and ROH.Vinyl formate gives a mixture of CH3CHO, Ni(CO)n(PR'3)4-n, C2H4, and CO2 on interaction with the Ni(0)-complexes. β-Lactones liberate CO2 on treatment with the Ni(0)-complexes.Oxidative addition of the reactants to Ni involving cleavage of the C-O bond(s) accounts for the formation of the products.
Insertion of Carbon Monoxide into Nickel-Alkyl Bonds of Monoalkyl- and Dialkylnickel(II) Complexes, NiR(Y)L2 and NiR2L2. Preparation of Ni(COR)(Y)L2 from NiR(Y)L2 and Selective Formation of Ketone, Diketone, and Aldehyde from NiR2L2
Yamamoto, Takakazu,Kohara, Teiji,Yamamoto, Akio
, p. 2161 - 2168 (2007/10/02)
Reactions of monoalkylnickel(II) complexes, NiR(Y)L2 (R=CH3, C2H5; Y=Cl, suc(succinimido), pht(phthalimido), OC6H4-p-CN; L=1/2 bpy (2,2'-bipyridine), PEt3 (triethylphosphine)), with CO afford monoacylnickel(II) complexes, Ni(COR)(Y)L2, which are characterized by elemental analysis and spectroscopies (IR and NMR).Reactions of the acylnickel(II) complexes with alcohols and aniline give the corresponding esters and amides, respectively.Exposure of Ni(COR)(Y)L2 to dry air leads to oxidation of RCO to a RCOO ligand giving a complex formulated as NI(OCOR)(Y)L2.Reactions of dimethylnickel(II) complexes, Ni(CH3)2L2 (L=1/2 bpy, PEt3, 1/2dpe (1,2-bis(diphenylphosphino)ethane, 1/2 dpp (1,3-bis(diphenylphosphino)propane), with carbon monoxide afford acetone and/or 2,3-butanedione in medium to high yields, the acetone/2,3-butanedione ratio varying with the ligand L, reaction temperature, and additives such as maleic anhydride and triphenylphosphine.Generally the acetone/2,3-butanedione ratio decreases with increase in thermal stabilities of Ni(CH3)2L2.Ni(C2H5)2(bpy) and Ni(n-C3H7)2(bpy) give 3-pentanone and 4-heptanone, respectively, on treating them with CO, whereas Ni(C2H5)2(dpe) produces C2H5CHO and C2H4.
