Studies of structural effects on the half-wave potentials of mononuclear and dinuclear nickel(II) diphosphine/dithiolate complexes

Kendra Redin, Aaron D. Wilson, Rachel Newell, M. Rakowski DuBois, Daniel L DuBois

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25 Citations (Scopus)

Abstract

Two series of mononuclear Ni(II) complexes of the formula (PNP)Ni(dithiolate) where PNP = R2PCH2N(CH 3)CH2-PR2, R = Et and Ph, have been synthesized containing dithiolate ligands that vary from five- to seven-membered chelate rings. Two series of dinuclear Ni(II) complexes of the formula {[(diphosphine)Ni]2(dithiolate)}(X)2 (X = BF4 or PF6) have been synthesized in which the chelate ring size of the dithiolate and diphosphine ligands have been systematically varied. The structures of the alkylated mononuclear complex, [(PNPEt)Ni(SC 2H4SMe)]OTf, and the dinuclear complex, [(dppeNi) 2(SC3H6S)](BF4)2, have been determined by X-ray diffraction studies. The complexes have been studied by cyclic voltammetry to determine how the half-wave potentials of the Ni(II/I) couples vary with chelate ring size of the ligands. For the mononuclear complexes, this potential becomes more positive as the natural bite angle of the dithiolate ligand increases. However, the potentials of the Ni(II/I) couples of the dinuclear complexes do not show a dependence on the chelate ring size of the ligands. Other aspects of the reduction chemistry of these complexes have been explored.

Original languageEnglish
Pages (from-to)1268-1276
Number of pages9
JournalInorganic Chemistry
Volume46
Issue number4
DOIs
Publication statusPublished - Feb 19 2007

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Nickel
chelates
nickel
Ligands
ligands
rings
Cyclic voltammetry
methylidyne
X ray diffraction
diffraction
x rays

ASJC Scopus subject areas

  • Inorganic Chemistry

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Studies of structural effects on the half-wave potentials of mononuclear and dinuclear nickel(II) diphosphine/dithiolate complexes. / Redin, Kendra; Wilson, Aaron D.; Newell, Rachel; DuBois, M. Rakowski; DuBois, Daniel L.

In: Inorganic Chemistry, Vol. 46, No. 4, 19.02.2007, p. 1268-1276.

Research output: Contribution to journalArticle

Redin, Kendra ; Wilson, Aaron D. ; Newell, Rachel ; DuBois, M. Rakowski ; DuBois, Daniel L. / Studies of structural effects on the half-wave potentials of mononuclear and dinuclear nickel(II) diphosphine/dithiolate complexes. In: Inorganic Chemistry. 2007 ; Vol. 46, No. 4. pp. 1268-1276.
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