22980-76-3

Upstream product

• 14783-10-9 [palladium(II)dichloride(1,10-phenanthroline)] 
• 15748-05-7 dichlorobis(1,10-phenanthroline)nickel(II) 
• 66-71-7 1,10-Phenanthroline 
• 83864-14-6 nickel dichloride 
• 29046-78-4 (1,2-dimethoxyethane)dichloronickel(II) 

Downstream Products

• 83864-14-6 nickel dichloride 
• 436154-25-5 Ni[PC₆H₅(C₆H₄S)2](1,10-phenanthroline) 

Relevant academic research and scientific papers

Mechanism of Nickel(II)-Catalyzed C(2)-H Alkynylation of Indoles with Alkynyl Bromide

The nickel system (THF)2NiBr2/phen has recently been shown as an efficient catalyst for the C-H bond alkynylation of diverse heteroarenes with (triisopropylsilyl)alkynyl bromide via monodentate chelation assistance. Herein, we report an extensive mechanistic investigation for the direct alkynylation of indoles involving the well-defined nickel catalyst, which features a coordinative insertion pathway of alkynyl bromide with the Ni(II) catalyst. Catalytic relevant nickel complexes, (phen)NiCl2 (5), (phen)2NiCl2 (6) and [(phen)3Ni]·NiCl4 (7) were isolated, and the complexes 6 and 7 were structurally characterized. Well-defined complexes were as competent as the in situ generated catalyst system (THF)2NiBr2/phen for the alkynylation of indoles. Various controlled studies and reactivity experiments were performed to understand the probable pathway for the alkynylation reaction. Kinetics analysis highlights that the complex (phen)NiX2 acts as a precatalyst, and the involvement of substrate indole and LiOtBu are essential for the generation of the active catalyst. Deuterium labeling and kinetic studies suggest that the process involving C-H cleavage and carbo-nickelation of indole is a crucial rate influencing step. Reactivity study of various alkynyl compounds with nickel-species highlights a migratory insertion route for the reaction. DFT calculations firmly support the experimental findings and suggest the coordinative insertion pathway of alkynyl bromide rather than oxidative addition toward the nickel(II) center.

Binuclear complex as well as preparation method and application thereof

The invention discloses a binuclear complex and a preparation method and application thereof. The binuclear complex comprises a structure shown in the following formula I or a structure shown in the following formula II shown in the specification, wherein M is a cobalt atom or a nickel atom. The invention provides a binuclear complex water oxidation catalyst with a novel structure, the water oxidation catalyst does not contain noble metals, and the prepared catalyst has good catalytic activity while the use of the noble metals is avoided, and has a good application prospect in the aspect of water oxidation catalysis.

Nickel(ii) and nickel(0) complexes as precursors of nickel nanoparticles for the catalytic hydrogenation of benzonitrile

The use of the nickel(ii) complex [(TEEDA)NiCl2] (1; TEEDA= N,N,N′,N′-tetraethyl-ethylendiamine) and nickel(0) complex [Ni(COD)2] (5) as pre-catalysts in the additive-free catalytic hydrogenation of benzonitrile (BN) is reported. In the presence of 1 (1 mol%), BN was hydrogenated under relatively mild reaction conditions (100 °C, 120 psi H2, 72 h) to the corresponding secondary imine, N-benzylidenebenzylamine (BBA), in very good yield (83%). As a counterpart, 5 (1 mol%) selectively hydrogenated BN to benzylamine (BA) in excellent yield (96%) under similar reaction conditions (80 °C, 120 psi H2, 24 h). In both cases, nickel nanoparticles (Ni-NPs) were identified as the catalytically active species. These Ni-NPs were formed in situ from 1 and 5 without external additives or additional stabilizers. The use of complex 5 was extended to the hydrogenation of different (hetero) aromatic and aliphatic nitriles.

Ni-Catalyzed β-Alkylation of Cyclopropanol-Derived Homoenolates

Metal homoenolates are valuable synthetic intermediates which provide access to β-functionalized ketones. In this report, we disclose a Ni-catalyzed β-alkylation reaction of cyclopropanol-derived homoenolates using redox-active N-hydroxyphthalimide (NHPI) esters as the alkylating reagents. The reaction is compatible with 1°, 2°, and 3° NHPI esters. Mechanistic studies imply radical activation of the NHPI ester and 2e β-carbon elimination occurring on the cyclopropanol.

1,10-Phenanthroline-dithiolate mixed ligand transition metal complexes. Synthesis, characterization and EPR spectroscopy

A series of new N2S2 mixed ligand transition metal complexes, where N2 is phenanthroline and S2 is 1,2-dithiooxalate (dto) or 1,2-dithiosquarate (dtsq), has been synthesized and characterized. IR spectra reveal that the 1,2-dithiolate ligands are coordinated via the sulfur atoms forming a N2S2 coordination sphere. The copper(II) complex [Cu(phen)(dto)] was studied by EPR spectroscopy as a diamagnetically diluted powder. The diamagnetic dilution resulted from doping of the copper complex into the isostructural host lattice of the nickel complex [Ni(phen)(dto)]. The electronic situation in the frontier orbitals of the copper complex calculated from the experimental data is compared to the results of EHT and DFT calculations. Furthermore, one side product, chlorobis(1,10-phenanthroline)copper(I) ethanol solvate hydrate [(phen)2CuCl]·C2H5OH·H2O, was formed by a reduction process and characterized by X-ray diffraction. In the crystal packing one-dimensional columns of dimers are formed, stabilized by significant π-π interactions.

Synthesis and reactivity of (chlorovinyl)nickel complexes: An unusual symmetrization reaction. X-ray crystal structure of [Ni(CCl=CCl2)2(PMe2Ph)2]

The oxidative addition of CCl2=CCl2, CCl2=CHCl, trans-CHCl=CHCl, and CH2=CCl2 to [Ni(PPh3)n], prepared in situ from NiCl2, PPh3, and NaBH4, gives square-planar trans-[NiCl]chlorovinyl)(PPh3)2]. The addition takes place at the less hindered C-Cl bond, with retention of geometry. The PPh3 ligand is replaced by dppe in [NiCl(C2Cl3)(PPh3)2] giving [NiCl(C2Cl3)dppe] whereas the action of N-donor bidentate ligands gives a symmetrization reaction, forming [NiCl2(LL)] and [Ni(C2Cl3)2(LL)] (LL = 2,2′-bpy and o-phen). The ligand bpy may be replaced by phosphines like PMe2Ph and PEt3 in the trichlorovinyl complex. The crystal structure of trans-[Ni(C2Cl3)2(PMe2Ph) 2] (monoclinic, space group P21/c, a = 9.203 (2) ?, b = 16.005 (3) ?, c = 9.604 (2) ?, β = 114.79 (3)°, Z = 2) shows the presence of the anti and syn isomere in the solid. The Ni-P bond distance and the mean Ni-C bond distance are 2.201 (1) and 1.91 (1) ?, respectively. 31P and 13C NMR spectra indicate that similar amounts of syn and anti isomers are present in solution.