Reversible sequential transfer of two electrons at the same potential in bis(1,3,5-triketonato)dicopper(II) complexes and their diamine Schiff bases. Effect of Na/sup +/ and similar ions on the cyclic voltammetry

Journal Article · Wed Mar 02 00:00:00 EST 1983 · Inorg. Chem.; (United States)

DOI:https://doi.org/10.1021/ic00147a018· OSTI ID:5555112

Lintvedt, R L; Kramer, L S

The cyclic voltammetry of four binuclear Cu(II) 1,3,5-triketonates and their diamine Schiff-base derivatives has been investigated in DMF with (C/sub 2/H/sub 5/)/sub 4/NClO/sub 4/ as the supporting electrolyte. Addition of simple cations such as Na/sup +/ to these solutions has a profound effect on the reduction potentials of the Cu(II) ions and on the stability of the reduced product. In the presence of a sufficient concentration of Na/sup +/ ions, the complexes exhibit one CV wave due to the coppers with peak separations of 42-44 mV and cathodic half-peak widths of 42-44 mV also. These results may be obtaned with no instrumental iR compensation, providing a high concentration of the supporting electrolyte is present. The process is reversible with use of the criteria of scan rate dependence of the cathodic peak current and width and the equivalence of the cathodic and anodic peak heights. Controlled-potential electrolysis results prove that the process involves the transfer of two electrons. All of the experimental facts may be explained by the reversible, sequential transfer of two electrons at the same potential. Although the two Cu(II) ions in the diamine Schiff bases are in much different coordination environments within the same molecule, they give rise to the same CV wave shapes as the triketonates; i,e., ..delta..E/sub p/ and E/sub pc/ - E/sub p///sub 2/ both are very nearly 42 mV. Thus, they also undergo two-electron transfer at the same potential. The only significant difference between the simpler binuclear Cu(II) triketonates and the diamine Schiff-base derivatives is that E/sub 1///sub 2/ values for the Schiff bases are about 0.1V more negative than for their triketonate analogues.

• Research Organization: Wayne State Univ., Detroit, MI
• OSTI ID: 5555112
• Journal Information: Inorg. Chem.; (United States), Vol. 22:5
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC
ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
COPPER COMPLEXES
ELECTROLYSIS
SCHIFF BASES
CATIONS
KETONES
ORGANOMETALLIC COMPOUNDS
SODIUM IONS
VOLTAMETRY
CHARGED PARTICLES
COMPLEXES
IMINES
IONS
LYSIS
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
TRANSITION ELEMENT COMPLEXES
400400* - Electrochemistry