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

Department of Chemistry

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

8 Citations (Scopus)

Abstract

In its neutral state, bis(diisopropylphosphino)amine HL reacts in equimolar amounts with the nickel halides NiCl₂·6H₂O, NiBr₂, and NiI₂in 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 NaNH₂followed by reaction with NiI₂gives 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 Ni⁰complex (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 CO₂reduction 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 - 2016

Keywords

COreactions
Electrochemistry
Nickel complexes
Phosphorus ligands
X-ray structures

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Inorganic Chemistry
Materials Chemistry

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@article{4bdef35cc4324cbd9adcd6342d866df5,

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 NiI2in 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 NaNH2followed by reaction with NiI2gives 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 Ni0complex (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 CO2reduction by the [(HL)2Ni]X2(X = BF4, NO3, ClO4) compounds.",

keywords = "COreactions, 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.}",

year = "2016",

doi = "10.1016/j.ica.2016.07.048",

language = "English",

volume = "453",

pages = "42--50",

journal = "Inorganica Chimica Acta",

issn = "0020-1693",

publisher = "Elsevier",

}

TY - JOUR

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

Y1 - 2016

N2 - In its neutral state, bis(diisopropylphosphino)amine HL reacts in equimolar amounts with the nickel halides NiCl2·6H2O, NiBr2, and NiI2in 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 NaNH2followed by reaction with NiI2gives 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 Ni0complex (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 CO2reduction 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 NiI2in 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 NaNH2followed by reaction with NiI2gives 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 Ni0complex (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 CO2reduction by the [(HL)2Ni]X2(X = BF4, NO3, ClO4) compounds.

KW - COreactions

KW - Electrochemistry

KW - Nickel complexes

KW - Phosphorus ligands

KW - X-ray structures

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U2 - 10.1016/j.ica.2016.07.048

DO - 10.1016/j.ica.2016.07.048

M3 - Article

AN - SCOPUS:84980324226

VL - 453

SP - 42

EP - 50

JO - Inorganica Chimica Acta

JF - Inorganica Chimica Acta

SN - 0020-1693

ER -