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

doi:10.1016/j.ica.2016.07.048

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 journal › Article

8 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 language	English
Pages (from-to)	42-50
Number of pages	9
Journal	Inorganica Chimica Acta
Volume	453
DOIs	https://doi.org/10.1016/j.ica.2016.07.048
Publication status	Published - Nov 1 2016

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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

Dickie, D. A., Chacon, B. E., Issabekov, A., Lam, K., & Kemp, R. A. (2016). Nickel(II) and nickel(0) complexes of bis(diisopropylphosphino)amine: Synthesis, structure, and electrochemical activity. Inorganica Chimica Acta, 453, 42-50. https://doi.org/10.1016/j.ica.2016.07.048

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title = "Nickel(II) and nickel(0) complexes of bis(diisopropylphosphino)amine: Synthesis, structure, and electrochemical activity",

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.",

keywords = "CO reactions, Electrochemistry, Nickel complexes, Phosphorus ligands, X-ray structures",

author = "Dickie, {Diane A.} and Chacon, {Brittany E.} and Alibek Issabekov and Kevin Lam and Kemp, {Richard A.}",

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T1 - Nickel(II) and nickel(0) complexes of bis(diisopropylphosphino)amine

T2 - Synthesis, structure, and electrochemical activity

AU - Dickie, Diane A.

AU - Chacon, Brittany E.

AU - Issabekov, Alibek

AU - Lam, Kevin

AU - Kemp, Richard A.

PY - 2016/11/1

Y1 - 2016/11/1

N2 - 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.

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.

KW - CO reactions

KW - Electrochemistry

KW - Nickel complexes

KW - Phosphorus ligands

KW - X-ray structures

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10.1016/j.ica.2016.07.048