Synthesis, structural characterization, and electrochemistry of (1)Metallocenophane complexes, (Si(alkyl)/sub 2/(C/sub 5/H/sub 4/)/sub 2/)MCl/sub 2/, M = Ti, Zr
A series of modified metallocene dichloride compounds, (SiR/sub 2/(C/sub 5/H/sub 4/)/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 evaluate the presence of a dialkylsilyl bridge on their electrochemical behavior. The 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 /sup 13/C NMR resonance of the bridgehead carbons is consistently located substantially upfield from the corresponding resonances for the proximal and distal carbons of the rings in these compounds. Cyclic voltammetric measurements have shown that these (1)metallocenophane dichlorides exhibit only one one-electron reversible reduction in THF within a scan range of +1.0 to -3.0 V 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 the 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 proceed similarly with the formation of only one paramagnetic product, (Si(CH/sub 3/)/sub 2/(C/sub 5/H/sub 4/)/sub 2/)MCl/sub 2//sup -/. The compounds (Si(CH/sub 3/)/sub 2/(C/sub 5/H/sub 4/)/sub 2/)MCl/sub 2/, M = Ti, Zr, similarly crystallize in a monoclinic unit cell of C2/c symmetry with the following refined lattice parameters: for M = Ti, a = 13.309 (5) A, b = 9.871 (2) a, c = 13.337 (4) A, ..beta.. = 132.79 (1)/sup 0/, V = 1285.8 (7) A/sup 3/, and rho/sub calcd/ = 1.576 g/cm/sup 3/; for M = Zr, a = 13.391 (3) A, b = 9.965 (2) A, c = 10.922 (3) A, ..beta.. = 113.37 (2) A, V = 1337.8 (5) A/sup 3/, and rho/sub calcd/ = 1.730 g/cm/sup 3/. 44 references, 6 figures, 7 tables.
- Research Organization:
- West Virginia Univ., Morgantown
- OSTI ID:
- 5826091
- Journal Information:
- Inorg. Chem.; (United States), Journal Name: Inorg. Chem.; (United States) Vol. 24:16; ISSN INOCA
- Country of Publication:
- United States
- Language:
- English
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360102 -- Metals & Alloys-- Structure & Phase Studies
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400301 -- Organic Chemistry-- Chemical & Physicochemical Properties-- (-1987)
400400* -- Electrochemistry
BOND ANGLE
BOND LENGTHS
CHEMICAL PREPARATION
CHEMICAL REACTIONS
CHEMISTRY
CHLORIDES
CHLORINE COMPOUNDS
COHERENT SCATTERING
COMPLEXES
DATA
DIFFRACTION
DIMENSIONS
ELECTROCHEMISTRY
ELECTRON SPIN RESONANCE
EXPERIMENTAL DATA
HALIDES
HALOGEN COMPOUNDS
INFORMATION
LATTICE PARAMETERS
LENGTH
MAGNETIC RESONANCE
MOLECULAR STRUCTURE
NMR SPECTRA
NUCLEAR MAGNETIC RESONANCE
NUMERICAL DATA
ORGANIC COMPOUNDS
REDUCTION
RESONANCE
SCATTERING
SILICON COMPLEXES
SPECTRA
SYNTHESIS
TITANIUM COMPLEXES
TRANSITION ELEMENT COMPLEXES
VOLTAMETRY
X-RAY DIFFRACTION
ZIRCONIUM COMPLEXES