Synthesis, characterization, and reactivity of (1)-metallocenophane complexes of titanium and zirconium
A series of modified metallocene dichloride compounds, (SiR/sub 2/(C/sub 2/H/sub 5/)/sub 2/)MCl/sub 2/ (M = Ti, R = CH/sub 3/; M = Zr, R = CH/sub 3/, C/sub 2/H/sub 5/, n-C/sub 3/H/sub 7/), have been prepared to investigate the stereochemical influence of the dialkylsilyl bridge on the chemical behavior of these modified metallocenes. These compounds have been characterized by elemental analysis and /sup 1/H and /sup 13/C NMR, and the molecular structures of (Si(CH/sub 3/)/sub 2/(C/sub 5/H/sub 4/)/sub 2/)MCl/sub 2/, M = Ti, Zr have been determined by X-ray diffraction methods. The susceptibility of these complexes to undergo reduction has been examined both by electrochemical and chemical means. Cyclic voltammetric measurements have shown that these (1)-metallocenophane dichlorides exhibit only one reversible reduction in THF within a scan range of 1.0 to -3.0 volts vs. SCE. Complementary EPR studies were conducted to identify and monitor the stability of the paramagnetic species generated during the electrochemical reduction of (Si(CH/sub 3/)/sub 2/(C/sub 5/H/sub 4/)/sub 2/)TiCl/sub 2/ and sodium naphthalide reduction of (Si(CH/sub 3/)/sub 2/(C/sub 5/H/sub 4/)/sub 2/)MCl/sub 2/, M = Ti, Zr. These reduction processes similarly proceed with the formation of only one stable paramagnetic product, (Si(CH/sub 3/)/sub 2/(C/sub 5/H/sub 4/)/sub 2/)MCl/sub 2/-.
- Research Organization:
- West Virginia Univ., Morgantown (USA)
- OSTI ID:
- 6950324
- Country of Publication:
- United States
- Language:
- English
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400201* -- Chemical & Physicochemical Properties
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ALKANES
CARBON 13
CARBON ISOTOPES
CHEMICAL ANALYSIS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
DATA
DIFFRACTION
ELECTROCHEMISTRY
ELECTRON SPIN RESONANCE
EVEN-ODD NUCLEI
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
HYDROCARBONS
HYDROGEN 1
HYDROGEN ISOTOPES
INFORMATION
ISOTOPES
LIGHT NUCLEI
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
NUCLEAR MAGNETIC RESONANCE
NUCLEI
NUMERICAL DATA
ODD-EVEN NUCLEI
ORGANIC COMPOUNDS
QUANTITATIVE CHEMICAL ANALYSIS
REDUCTION
RESONANCE
SCATTERING
STABLE ISOTOPES
STEREOCHEMISTRY
SYNTHESIS
TITANIUM COMPOUNDS
TRANSITION ELEMENT COMPOUNDS
VOLTAMETRY
X-RAY DIFFRACTION
ZIRCONIUM COMPOUNDS