Synthesis, characterization, and electrochemical studies of iron, cobalt, and nickel complexes of polyphosphine ligands

Daniel L DuBois, Alex Miedaner

Research output: Contribution to journalArticle

53 Citations (Scopus)

Abstract

The reaction of [M(CH3CN)6](BF4)2 (where M = Fe, Co, and Ni) with P(CH2CH2PPh2)3 (PP3), PhP(CH2CH2PPh2)2 (PP2), and Ph2PCH2CH2PPh2 (dppe) results in the formation of [Fe(PP3)(CH3CN)2](BF4)2, [Fe(PP2)(CH3CN)3](BF4)2, [Fe(dppe)2-(CH3CN)2](BF4) 2, [Co(PP3)(CH3CN)](BF4)2, [Co(dppe)2(CH3CN)](BF4)2, [Ni(PP3)(CH3CN)](BF4)2, [Ni(PP2)(CH3CN)]-(BF4)2, and [Ni(dppe)2](BF4)2, respectively. Electrochemical studies have been carried out on these complexes to examine the influence of the nature of the polyphosphine ligand on the redox properties of each metal. For [Fe(PP3)(CH3CN)2](BF4)2 the reversibility of both the Fe(II/III) and Fe(I/0) couples are enhanced relative to those of [Fe(dppe)2(CH3CN)2](BF4) 2. For [Co(PP3)(CH3CN)](BF4)2 the lowest oxidation state accessible in CH3CN is +1, while for [Co(dppe)2(CH3CN)](BF4)2 the -1 oxidation state can be observed. The Ni(I/0) couple is reversible for [Ni(dppe)2](BF4)2 and irreversible for [Ni(PP2)(CH3C-N)](BF4)2 and [Ni(PP3)(CH3CN)](BF4)2. The electrochemical studies of the latter complex have led to the synthesis of a Ni(0) dimer, [Ni(PP3)]2.

Original languageEnglish
Pages (from-to)4642-4650
Number of pages9
JournalInorganic Chemistry
Volume25
Issue number26
Publication statusPublished - 1986

ASJC Scopus subject areas

  • Inorganic Chemistry

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