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

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 ORCID: 0000-0003-1481-9212 and Kemp, Richard A. (2016) Nickel(II) and nickel(0) complexes of bis(diisopropylphosphino)amine: Synthesis, structure, and electrochemical activity. Inorganica Chimica Acta, 453. pp. 42-50. ISSN 0020-1693 (doi:https://doi.org/10.1016/j.ica.2016.07.048)

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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 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)2NiX2(X = BF4, NO3, ClO4) were prepared from 2:1 ligand-metal ratios of Ni(BF4)2{\textperiodcentered}6H2O, Ni(NO3)2{\textperiodcentered}6H2O, or Ni(ClO4)2{\textperiodcentered}6H2O. Deprotonation of the ligand with NaNH2followed by reaction with NiI2gives L2Ni when performed in Et2O, but leads to the co-crystal L2Ni{\textperiodcentered}2NCCHC(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)2NiX2(X = BF4, NO3, ClO4) compounds.

Item Type: Article
Uncontrolled Keywords: CO2reactions, Electrochemistry, Nickel complexes, Phosphorus ligands, X-ray structures
Subjects: Q Science > QC Physics
Q Science > QD Chemistry
Faculty / Department / Research Group: Faculty of Engineering & Science
Faculty of Engineering & Science > Department of Pharmaceutical, Chemical & Environmental Sciences
Last Modified: 30 Jul 2018 00:38
Selected for GREAT 2016: None
Selected for GREAT 2017: None
Selected for GREAT 2018: None
Selected for GREAT 2019: None
URI: http://gala.gre.ac.uk/id/eprint/17711

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