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 | |
| 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
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 journal › Article
}
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 - 2016/11/1
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
UR - http://www.scopus.com/inward/record.url?scp=84980324226&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=84980324226&partnerID=8YFLogxK
U2 - 10.1016/j.ica.2016.07.048
DO - 10.1016/j.ica.2016.07.048
M3 - Article
VL - 453
SP - 42
EP - 50
JO - Inorganica Chimica Acta
JF - Inorganica Chimica Acta
SN - 0020-1693
ER -