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.
N1 - Funding Information:
Dr. Beth Donovan (UNM) and Mr. Nate Wilson (SNL) performed preliminary electrochemical experiments on 5. Mr. Jeremiah Sears (SNL) performed the elemental analysis on compounds 7 and 7a. This work was financially supported by the National Science Foundation (Grant CHE12-13529), the Sandia National Laboratories-sponsored STAR Summer Fellows program, and the Kazakh Ministry of Education and Science. The Bruker X-ray diffractometer was purchased via a National Science Foundation CRIF:MU award to the University of New Mexico (CHE04-43580), and the NMR spectrometers were upgraded via grants from the NSF (CHE08-40523 and CHE09-46690). Sandia is a multiprogram laboratory operated by Sandia Corporation, a Lockheed Martin Company, for the U.S. Department of Energy's National Nuclear Security Administration under Contract DE-AC04-94-AL85000.
Publisher Copyright:
© 2016 Elsevier B.V.
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 -