917-57-7Relevant articles and documents
West,Glaze
, p. 2096 (1961)
Synthesis and Reactivity of Reduced α-Diimine Nickel Complexes Relevant to Acrylic Acid Synthesis
Joannou, Matthew V.,Bezdek, Máté J.,Albahily, Khalid,Korobkov, Ilia,Chirik, Paul J.
supporting information, p. 3389 - 3393 (2018/10/31)
The aryl-substituted α-diimine (DI) nickel vinyl complex (iPrDI)Ni(CH=CH2) (iPrDI = [2,6-(iPr)2C6H3N=C(CH3)]2) was synthesized and structurally characterized. The complex is dimeric in the solid state and has a distorted-square-planar geometry at nickel. A combination of single-crystal X-ray diffraction, EPR, magnetic susceptibility, and NMR analyses was used to elucidate the electronic structure of the compound, and it is best described as a low-spin Ni(II) derivative with a singly reduced α-diimine chelate. Addition of CO2 to the nickel vinyl complex resulted in insertion into the nickel-carbon bond to yield the corresponding nickel acrylate (iPrDI)Ni(κ2-O2CCH=CH2). EPR spectroscopy coupled with DFT calculations established that the S = 1/2 product maintains the nickel(II) oxidation state with an α-diimine-centered radical. Addition of acrylic acid to (iPrDI)Ni(CH=CH2) induced rapid, net bimetallic reductive elimination to release butadiene and produced the metastable olefin-bound acrylic acid complex (iPrDI)Ni(κ2-CH2=CHCO2H). Over the course of 2 h at 23 °C, this complex underwent a net oxidation to produce (iPrDI)Ni(κ2-O2CCH=CH2), with concomitant loss of H2.
Enantioselective Conjunctive Cross-Coupling of Bis(alkenyl)borates: A General Synthesis of Chiral Allylboron Reagents
Edelstein, Emma K.,Namirembe, Sheila,Morken, James P.
supporting information, p. 5027 - 5030 (2017/05/04)
Palladium-catalyzed conjunctive cross-coupling is used for the synthesis of enantioenriched allylboron reagents. This reaction employs nonsymmetric bis(alkenyl)borates as substrates and appears to occur by a mechanism that involves selective activation of the less substituted alkene followed by migration of the more substituted alkene during the course of a Pd-induced metalate rearrangement.