D. Cam et al., REDUCTION OF BIS(ETA-5-CYCLOPENTADIENYL)ZIRCONIUM DICHLORIDE IN THE PRESENCE OF METHYLALUMOXANE, Macromolecular chemistry and physics, 195(8), 1994, pp. 2817-2826
The reaction occurring between bis(eta5-C5H5)ZrCl2 (C5H5 = cyclopentad
ienyl) and methylalumoxane (MAO) has been studied by means of electron
paramagnetic resonance (EPR) spectroscopy at different zirconium conc
entrations and Al/Zr mole ratios. The toluene solution of bis(eta5-C5H
5)ZrCl2/methylalumoxane, in the absence of ethylene, was verified to b
e more stable than the catalytic system based on bis(eta5-C5H5)TiCl2/A
lR3 (R = alkyl). Zr(IV) was reduced to Zr(III) in small amounts with a
Lande factor g = 1,998 and a hyperfine interaction splitting constant
alpha (Zr-91) = 7 G. The presence of ethylene strongly increased the
efficiency of the Zr(IV) to Zr(III) reduction. Simultaneously it modif
ied the chemical electronic surrounding of the Zr nucleus as revealed
by the sharp increase of a (Zr-91) = 12 G.