Synthesis and Reactivity of Reduced α-Diimine Nickel Complexes Relevant to Acrylic Acid Synthesis

Matthew V. Joannou; Máté J. Bezdek; Khalid Albahily; Ilia Korobkov; Paul J. Chirik

doi:10.1021/acs.organomet.8b00350

Synthesis and Reactivity of Reduced α-Diimine Nickel Complexes Relevant to Acrylic Acid Synthesis

Matthew V. Joannou, Máté J. Bezdek, Khalid Albahily, Ilia Korobkov, Paul J. Chirik

Chemistry

Research output: Contribution to journal › Article › peer-review

20 Scopus citations

Abstract

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.

Original language	English (US)
Pages (from-to)	3389-3393
Number of pages	5
Journal	Organometallics
Volume	37
Issue number	20
DOIs	https://doi.org/10.1021/acs.organomet.8b00350
State	Published - Oct 22 2018

All Science Journal Classification (ASJC) codes

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Synthesis and Reactivity of Reduced α-Diimine Nickel Complexes Relevant to Acrylic Acid Synthesis",

abstract = "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.",

author = "Joannou, {Matthew V.} and Bezdek, {M{\'a}t{\'e} J.} and Khalid Albahily and Ilia Korobkov and Chirik, {Paul J.}",

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T1 - Synthesis and Reactivity of Reduced α-Diimine Nickel Complexes Relevant to Acrylic Acid Synthesis

AU - Joannou, Matthew V.

AU - Bezdek, Máté J.

AU - Albahily, Khalid

AU - Korobkov, Ilia

AU - Chirik, Paul J.

PY - 2018/10/22

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N2 - 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.

AB - 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.

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Synthesis and Reactivity of Reduced α-Diimine Nickel Complexes Relevant to Acrylic Acid Synthesis

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