Electrochemistry of metallocene dichlorides of subgroup IVB in tetrahydrofuran

Journal Article · Mon Nov 10 04:00:00 UTC 1986 · Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States)

DOI:https://doi.org/10.1007/BF00955351· OSTI ID:6476622

Kukharenko, S V; Soloveichik, G L; Strelets, V V

The complex metallocenyl chlorides Cp/sub 2/MCl/sub 2/ (M = Ti, Zr, Hf) are reversibly reduced in a THF medium on a dropping mercury electrode to the corresponding metastable radical anions Cp/sub 2/MCl/sub 2//sup -./, which are reversibly converted into the complexes Cp/sub 2/MCl, the rate of the dehalogenation reaction decreases as the temperature is lowered and increases along the series of metals Zr..-->.. Hf ..-->.. Ti. The second reduction wave of the complexes Cp/sub 2/MCl/sub 2/ corresponds to the irreversible one-electron reduction of the complexes Cp/sub 2/MCl/sub 2/, which form in the layer next to the electrode as a result of the dehalogenation of Cp/sub 2/MCl/sub 2//sup -./. The third wave corresponds to the one-electron reduction of the radical anions Cp/sub 2/MCl/sub 2//sup -./ (M = Zr, Hf) or titanocene (M = Ti). The electroreduction of the complexes Cp/sub 2/MCl/sub 2/ to the M(III) and M(II) derivatives becomes increasingly hindered along the series Ti ..-->.. Zr..-->.. Hf. The values of E/sub 1/2/ of the complexes studied are linearly correlated with the fourth and third ionization potentials of the corresponding metals in the gaseous phase.

• Research Organization: Institute of Chemical Physics, Chernogolovka, USSR
• OSTI ID: 6476622
• Journal Information: Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States), Journal Name: Bull. Acad. Sci. USSR, Div. Chem. Sci. (Engl. Transl.); (United States) Vol. 35:5; ISSN BACCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
400400 -- Electrochemistry
ALKENES
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE COMPOUNDS
CHROMIUM COMPLEXES
CHROMIUM COMPOUNDS
CHROMIUM IODIDES
COMPARATIVE EVALUATIONS
COMPLEXES
COMPLEXOMETRY
CYCLOALKENES
CYCLOPENTADIENE
DECHLORINATION
DEHALOGENATION
DIENES
DIFFUSION
ELECTROCHEMISTRY
ELECTROLYTES
ELECTRON TRANSFER
HAFNIUM CHLORIDES
HAFNIUM COMPLEXES
HAFNIUM COMPOUNDS
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
IODIDES
IODINE COMPOUNDS
IONIZATION POTENTIAL
ORGANIC COMPOUNDS
POLAROGRAPHY
POLYENES
REDUCTION
REFRACTORY METAL COMPOUNDS
TEMPERATURE DEPENDENCE
TITANIUM CHLORIDES
TITANIUM COMPLEXES
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPLEXES
TRANSITION ELEMENT COMPOUNDS
VOLTAMETRY
ZIRCONIUM CHLORIDES
ZIRCONIUM COMPLEXES
ZIRCONIUM COMPOUNDS