12151-13-2

Upstream product

• 1295-35-8 bis(1,5-cyclooctadiene)nickel ⁽⁰⁾ 
• 6140-80-3 3-isopropoxyprop-1-ene 
• 627-40-7 methylallylether 
• 23777-40-4 bis(triphenylphosphine)ethylenenickel⁽⁰⁾ 
• 5259-72-3 cyclo-octa-1,5-diene 
• 603-35-0 triphenylphosphine 

Downstream Products

• 14264-16-5 bis(triphenylphosphine)nickel(II) chloride 
• 13007-90-4 bis(triphenylphosphine)nickel⁽⁰⁾ dicarbonyl 
• 206866-49-1 Ni(P(C₆H₅)3)2((13C)-carbon monoxide)2 
• 1111-72-4 carbon dioxide 
• 5259-72-3 cyclo-octa-1,5-diene 
• 106108-33-2 (η2-styrene)bis(triphenylphosphine)nickel(0) 
• 133090-87-6 {(C₆H₅)3P}2Ni{P(Cl)N(C₆H₂)(C₄H₉)3}2 
• 149669-69-2 ((C₆H₅)3P)2Ni(BrPNC₆H₂(C(CH₃)3)3) 
• 149669-70-5 ((C₆H₅)3P)2Ni(IPNC₆H₂(C(CH₃)3)3) 
• 1227945-10-9 (Ph3P)Ni(η3-PhCCB(C6F5)2) 
• 900517-88-6 bis(triethoxysilyl)bis(triphenylphosphine) 
• 13007-90-4 cis-Ni(CO)2{P(C₆H₅)3}2 
• 154827-02-8 ((C₆H₅)3P)3NiPC(Si(CH₃)3)2⁽¹⁺⁾*AlCl₄^(1-)={((C₆H₅)3P)3NiPC(Si(CH₃)3)2}{AlCl₄} 

Relevant academic research and scientific papers

Tandem Nickel-Catalyzed Dimerization/(4+2) Cycloaddition of Terminal Alkynes with Four-Membered Ring Ketones

Controlling the behavior of terminal alkynes in metal-catalyzed intermolecular tandem reactions is a formidable challenge despite the potential advantage offered by these strategies in modern synthesis. Herein, we describe that a nickel catalyst enables a tandem process involving the rapid dimerization of terminal alkynes into 1,3-enynes and the cycloaddition of these intermediates with an azetidinone, an oxetanone or benzocyclobutenones. Significantly, the slow or sequential addition of reagents and catalysts is not required to orchestrate their reactivity. These results are in stark contrast with previous cycloadditions of terminal alkynes with strained four-membered ring substrates, which previously led to oligomerization or cyclotrimerization, except in the case of tert-butylacetylene.

AIR-STABLE NI(0)-OLEFIN COMPLEXES AND THEIR USE AS CATALYSTS OR PRECATALYSTS

The present invention relates to air stable, binary Ni(0)-olefin complexes and their use in organic synthesis.

Synergy between Experimental and Computational Chemistry Reveals the Mechanism of Decomposition of Nickel-Ketene Complexes

A series of (dppf)Ni(ketene) complexes were synthesized and fully characterized. In the solid state, the complexes possess η2-(C,O) coordination of the ketene in an overall planar configuration. They display similar structure in solution, except in some cases, the η2-(C,C) coordination mode is also detected. A combination of kinetic analysis and DFT calculations reveals the complexes undergo thermal decomposition by isomerization from η2-(C,O) to η2-(C,C) followed by scission of the C=C bond, which is usually rate limiting and results in an intermediate carbonyl carbene complex. Subsequent rearrangement of the carbene ligand is rate limiting for electron poor and sterically large ketenes, and results in a carbonyl alkene complex. The alkene readily dissociates, affording alkenes and (dppf)Ni(CO)2. Computational modeling of the decarbonylation pathway with partial phosphine dissociation reveals the barrier is reduced significantly, explaining the instability of ketene complexes with monodentate phosphines.

Intermediates in nickel(0)-phosphine complex catalyzed dehydrogenative silylation of olefins

Nickel(0) complexes 1-4 containing π-coordinated olefin and triphenylphosphine (tricyclohexylphosphine) (starting from Ni(cod)2) were prepared and the X-ray structures of 1 and 2 were resolved. The complexes appeared as efficient catalysts in d

Interaction of Nickel(0) Complexes with Allyl Carboxylates, Allyl Ethers, Allylic Alcohols, and Vinyl Acetate. ?-Complex Formation and Oxidative Addition to Nickel Involving Cleavage of the Alkenyl-Oxygen Bond

Interaction of various allylic compounds with bis(1,5-cyclooctadiene)nickel, Ni(cod)2, in the absence and presence of tertiary phosphines, causes cleavage of allyl-oxygen bonds.Allyl acetate reacts with Ni(cod)2 to afford a mixture of Ni(η3-C3H5)2 and Ni(OCOCH3)2 presumably through an intermediate, allylnickel acetate, followed by its disproportionation.Similar reactions in the presence of tertiary phosphine ligands, PR3 (triphenylphosphine (PPh3), ethyldiphenylphosphine (PEtPh2), tricyclohexylphosphine (P-c-Hx3)), give Ni(η3-C3H5(OCOCH3)(PR3) (1-3).Allyl formate can be catalytically converted into propylene and CO2 at 25 deg C by a Ni(cod)2-PPh3 mixture.A reaction of allyl phenyl ether with a mixture of Ni(cod)2 and PPh3 at 30 deg C also leads to cleavage of the C-O bond to yield Ni(η3-C3H5)(OC6H5)(PPh3) (4).Complexes 1-4 react with morpholine to produce N-allylmorpholine in 65-82percent yields.On the other hand, similar reactions of diallyl ether with mixtures of Ni(cod)2 and phosphine ligands do not cause C-O bond cleavage under mild conditions and yield complexes formulated as Ni(?-diallyl ether)(PR3) (PR3 = PPh3, P-c-Hx3) (5 and 6).Allylic alcohols RCH=CHCH2OH (R = H, CH3, C6H5) are dismutated into RCH=CHCH3, RCH=CHCHO, and H2O on interaction with mixtures of Ni(cod)2 and phosphines at 30-50 deg C.The mixture of Ni(cod)2 and PPh3 serves as a catalyst for the allylation of morpholine by allyl alcohol.The C-O bond in vinyl acetate is also cleaved on interaction with Ni(cod)2 alone or mixtures of Ni(cod)2 and phosphines.Complexes 1-6 are characterized by elemental analysis and spectroscopy (IR and NMR).As for the mechanism of the C-O bond-cleavage reaction of allyl-oxygen compounds, one involving coordination of the allylic compound to Ni through the C=C double bond followed by a bond rearrangement involving C-O bond cleavage is proposed.