Nickel(II) and nickel(0) complexes of bis(diisopropylphosphino)amine

Synthesis, structure, and electrochemical activity

Diane A. Dickie, Brittany E. Chacon, Alibek Issabekov, Kevin Lam, Richard A. Kemp

    Research output: Contribution to journalArticle

    7 Citations (Scopus)

    Abstract

    In its neutral state, bis(diisopropylphosphino)amine HL reacts in equimolar amounts with the nickel halides NiCl2·6H2O, NiBr2, and NiI2 in ethanol solutions to give the air- and moisture-stable P,P-chelated complexes (HL)NiX2 (X = Cl, Br, I). Under similar conditions, complexes of the form [(HL)2Ni]X2 (X = BF4, NO3, ClO4) were prepared from 2:1 ligand-metal ratios of Ni(BF4)2·6H2O, Ni(NO3)2·6H2O, or Ni(ClO4)2·6H2O. Deprotonation of the ligand with NaNH2 followed by reaction with NiI2 gives L2Ni when performed in Et2O, but leads to the co-crystal L2Ni·2[NCCHC(Me)NH2] when the solvent is acetonitrile. In addition to these Ni2+ compounds, the Ni0 complex (HL)2Ni can be prepared from a toluene solution of Ni(cod)2. Each complex has been characterized by a combination of IR and multi-nuclear NMR spectroscopies, as well as single-crystal X-ray diffraction. Electrochemical studies of the complexes revealed irreversible decomposition of the (HL)NiX2 (X = Cl, Br, I) series, but electrocatalytic CO2 reduction by the [(HL)2Ni]X2 (X = BF4, NO3, ClO4) compounds.

    Original languageEnglish
    Pages (from-to)42-50
    Number of pages9
    JournalInorganica Chimica Acta
    Volume453
    DOIs
    Publication statusPublished - Nov 1 2016

    Fingerprint

    Nickel
    Amines
    amines
    Ligands
    nickel
    Deprotonation
    ligands
    synthesis
    Acetonitrile
    moisture
    Nuclear magnetic resonance spectroscopy
    acetonitrile
    halides
    Toluene
    toluene
    Ethanol
    ethyl alcohol
    Moisture
    Single crystals
    Decomposition

    Keywords

    • CO reactions
    • Electrochemistry
    • Nickel complexes
    • Phosphorus ligands
    • X-ray structures

    ASJC Scopus subject areas

    • Inorganic Chemistry
    • Physical and Theoretical Chemistry
    • Materials Chemistry

    Cite this

    Nickel(II) and nickel(0) complexes of bis(diisopropylphosphino)amine : Synthesis, structure, and electrochemical activity. / Dickie, Diane A.; Chacon, Brittany E.; Issabekov, Alibek; Lam, Kevin; Kemp, Richard A.

    In: Inorganica Chimica Acta, Vol. 453, 01.11.2016, p. 42-50.

    Research output: Contribution to journalArticle

    Dickie, Diane A. ; Chacon, Brittany E. ; Issabekov, Alibek ; Lam, Kevin ; Kemp, Richard A. / Nickel(II) and nickel(0) complexes of bis(diisopropylphosphino)amine : Synthesis, structure, and electrochemical activity. In: Inorganica Chimica Acta. 2016 ; Vol. 453. pp. 42-50.
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    abstract = "In its neutral state, bis(diisopropylphosphino)amine HL reacts in equimolar amounts with the nickel halides NiCl2·6H2O, NiBr2, and NiI2 in ethanol solutions to give the air- and moisture-stable P,P-chelated complexes (HL)NiX2 (X = Cl, Br, I). Under similar conditions, complexes of the form [(HL)2Ni]X2 (X = BF4, NO3, ClO4) were prepared from 2:1 ligand-metal ratios of Ni(BF4)2·6H2O, Ni(NO3)2·6H2O, or Ni(ClO4)2·6H2O. Deprotonation of the ligand with NaNH2 followed by reaction with NiI2 gives L2Ni when performed in Et2O, but leads to the co-crystal L2Ni·2[NCCHC(Me)NH2] when the solvent is acetonitrile. In addition to these Ni2+ compounds, the Ni0 complex (HL)2Ni can be prepared from a toluene solution of Ni(cod)2. Each complex has been characterized by a combination of IR and multi-nuclear NMR spectroscopies, as well as single-crystal X-ray diffraction. Electrochemical studies of the complexes revealed irreversible decomposition of the (HL)NiX2 (X = Cl, Br, I) series, but electrocatalytic CO2 reduction by the [(HL)2Ni]X2 (X = BF4, NO3, ClO4) compounds.",
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    T2 - Synthesis, structure, and electrochemical activity

    AU - Dickie, Diane A.

    AU - Chacon, Brittany E.

    AU - Issabekov, Alibek

    AU - Lam, Kevin

    AU - Kemp, Richard A.

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    AB - In its neutral state, bis(diisopropylphosphino)amine HL reacts in equimolar amounts with the nickel halides NiCl2·6H2O, NiBr2, and NiI2 in ethanol solutions to give the air- and moisture-stable P,P-chelated complexes (HL)NiX2 (X = Cl, Br, I). Under similar conditions, complexes of the form [(HL)2Ni]X2 (X = BF4, NO3, ClO4) were prepared from 2:1 ligand-metal ratios of Ni(BF4)2·6H2O, Ni(NO3)2·6H2O, or Ni(ClO4)2·6H2O. Deprotonation of the ligand with NaNH2 followed by reaction with NiI2 gives L2Ni when performed in Et2O, but leads to the co-crystal L2Ni·2[NCCHC(Me)NH2] when the solvent is acetonitrile. In addition to these Ni2+ compounds, the Ni0 complex (HL)2Ni can be prepared from a toluene solution of Ni(cod)2. Each complex has been characterized by a combination of IR and multi-nuclear NMR spectroscopies, as well as single-crystal X-ray diffraction. Electrochemical studies of the complexes revealed irreversible decomposition of the (HL)NiX2 (X = Cl, Br, I) series, but electrocatalytic CO2 reduction by the [(HL)2Ni]X2 (X = BF4, NO3, ClO4) compounds.

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    KW - Phosphorus ligands

    KW - X-ray structures

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