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

Journal Article · Wed Dec 17 00:00:00 EST 1986 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00246a011· OSTI ID:6713391

DuBois, D L; Miedaner, A

The reaction of (M(CH/sub 3/CN)/sub 6/) (BF/sub 4/)/sub 2/ (where M = Fe, Co, and Ni) with P(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 3/ (PP/sub 3/), PhP(CH/sub 2/CH/sub 2/PPh/sub 2/)/sub 2/ (PP/sub 2/), and Ph/sub 2/PCH/sub 2/CH/sub 2/PPh/sub 2/ (dppe) results in the formation of (Fe(PP/sub 3/)(CH/sub 3/CN)/sub 2/) (BF/sub 4/)/sub 2/, (Fe(PP/sub 2/)(CH/sub 3/CN)/sub 3/) (BF/sub 4/)/sub 2/, (Fe(dppe)/sub 2/(CH/sub 3/CN)/sub 2/) (BF/sub 4/)/sub 2/, (Co(PP/sub 3/)(CH/sub 3/CN)) (BF/sub 4/)/sub 2/, (Co(dppe)/sub 2/(CH/sub 3/CN)) (BF/sub 4/)/sub 2/, (Ni(PP/sub 3/)(CH/sub 3/CN)) (BF/sub 4/)/sub 2/, (Ni(PP/sub 2/)(CH/sub 3/CN))(BF/sub 4/)/sub 2/, and (Ni(dppe)/sub 2/)(BF/sub 3/)/sub 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(PP)(CH/sub 3/CN)/sub 2/)(BF/sub 4/)/sub 2/ the reversibility of both the Fe(II/III) and Fe(I/0) couples are enhanced relative to those of (Fe(dppe)/sub 2/(CH/sub 3/CN)/sub 2/)(BF/sub 4/)/sub 2/. For (Co(PP/sub 3/)(CH/sub 3/CN))(BF/sub 4/)/sub 2/ the lowest oxidation state accessible in CH/sub 3/CN is +1, while for (Co(dppe)/sub 2/(CH/sub 3/CN))(BF/sub 4/)/sub 2/ the -1 oxidation state can be observed. The Ni(I/0) couple is reversible for (Ni(dppe)/sub 2/)(BF/sub 4/)/sub 2/ and irreversible for (Ni(PP/sub 2/)(CH/sub 3/CN))(BF/sub 4/)/sub 2/ and (Ni(PP/sub 3/)(CH/sub 3/CN))(BF/sub 4/)/sub 2/. The electrochemical studies of the latter complex have led to the synthesis of a Ni(0) dimer, (Ni(PP/sub 3/))/sub 2/.

• Research Organization: Solar Energy Research Institute, Golden, CO
• OSTI ID: 6713391
• Journal Information: Inorg. Chem.; (United States), Vol. 25:26
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
CARBONYLS
BOND LENGTHS
HEME
IRON COMPLEXES
PORPHYRINS
EXPERIMENTAL DATA
CARBOXYLIC ACIDS
COMPLEXES
DATA
DIMENSIONS
HETEROCYCLIC ACIDS
HETEROCYCLIC COMPOUNDS
INFORMATION
LENGTH
NUMERICAL DATA
ORGANIC ACIDS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PIGMENTS
TRANSITION ELEMENT COMPLEXES
400201* - Chemical & Physicochemical Properties