Abstract
DFT quantum-chemical calculations have been performed to elucidate the geometrical and electronic structure of methylalumoxanes (-Al(Me)0-)n with different size (n=6,8,12). The three-dimensional oxo-bridged (cage) structures of methylalumoxane (MAO) have been analyzed.
It has been found that the cage structure consisting of three layers of [-Al(CH)30-]4 units is the most stable for MAO with n=12. Trimethylaluminium reacts with MAO by cleavage of a Al-O dative bond and the formation of acidic tricoordinated Al-atoms and basic dicoordinated O-atoms in the MAO molecule. Two molecules of AlMe3 are associated with these sites. The total heat of the TMA interaction with MAO depends on the n value and the MAO structure. The reactive sites of MAO are proposed based on the obtained data.
This is a preview of subscription content, log in via an institution to check access.
Access this chapter
Tax calculation will be finalised at checkout
Purchases are for personal use only
Preview
Unable to display preview. Download preview PDF.
Similar content being viewed by others
References
H. Sinn, W. Kaminsky, Adv.Organomet.Chem. 18, 99 (1980)
W. Kaminsky, M. Miri, H. Sinn, R. Woldt, Macromol.Chem.Rapid Commun. 4, 417(1983)
R.F. Jordan, Adv.Organomet.Chem. 32, 325 (1991)
C. Sishta, R.H. Hathorn, T.J. Marks, J. Am. Chem. Soc. 114, 1112 (1992)
X. Yang, C.L. Stern, T.J. Marks, J. Am. Chem. Soc. 116, 10015 (1994)
M. Bochmann, S.J. Lancaster, Angew. Chem., Int. Ed. Engl., 33, 1634 (1994)
I. Tritto, M.C. Sacchi, G. Zannoni, Macromolecules 26, 7112 (1993)
I. Tritto, M.C. Sacchi, S. Li, Macromol. Rapid Commun. 15, 217 (1994)
I. Tritto, R. Donetti, M.C. Sacchi, P. Locatelli, G. Zannoni, Macromolecules 30, 1247(1997)
K.Q. Peng, S.J. Xiao, J. Mol. Catal., 90, 201 (1994)
E. Giannetti, G.M. Nicoletti, R. Mazzochi, J. Polym. Sci., Polym. Chem. Ed., 23, 2117 (1985)
H. Sinn, Macromol Symp. 97, 27 (1995)
I. Tritto, C. Mealares, M.C. Sacchi, P. Locatelli, Macromol. Chem. Phys. 198, 3963 (1997)
S. Reddy, G. Shaashider, S. Sivaram, Macromolecules 26, 1180 (1993)
B. Reiger, C. Janiak, Angew. Makromol Chem., 215, 35 (1994)
M.R. Mason, J.M. Smith, S.G. Bott, A.R. Barron, J. Am. Chem. Soc. 115, 4971 (1993)
D.E. Babushkin, N.V. Semikolenova, V.N. Panchenko, A.P. Sobolev, V.A. Zakharov, E.P. Talsi, Macromol. Chem. Phys. 198, 3845 (1997)
E.P. Talsi, N.V. Semikolenova, V.N. Panchenko, A.P. Sobolev, D.E. Babushkin, A.A. Shubin, V.A. Zakharov, J. Mol Catal, in press
I.I. Zakharov, V.A. Zakharov, G.M. Zhidomiriv, Macromol. Theory Simul. (1999) in press
M.J. Frisch, G.W. Trucks, H.B. Schlegel, P.M.W. Gill, B.G. Johnson, M.W. Wong, J.B. Foresman, M.A. Robb, M. Head-Gordon, E S. Replogle, R. Gomperts, J.L. Andres, K. Raghavachari, J.S. Binkley, C. Gonzalez, L. Martin, D.J. Fox, D.J. Defrees, J. Baker, J.J.P. Stewart, J. A. Pople, Gaussian 92/DFT, Revision G.2, Gaussian, Inc., Pittsburgh PA, 1993.
P.J. Hay, W.R. Wadt, J. Chem. Phys. 82, 270 (1985)
S.J. Vosco, L. Wilk, M. Nusair, Can. J. Phys. 58, 1200 (1980)
P.H. Lewis, R.E. Rundle, J.Chem.Phys. 21, 986 (1953)
M.B. Smith, J. Organomet. Chem. 70, 13 (1974)
Author information
Authors and Affiliations
Editor information
Editors and Affiliations
Rights and permissions
Copyright information
© 1999 Springer-Verlag Berlin Heidelberg
About this paper
Cite this paper
Zakharov, I.I., Zakharov, V.A., Zhidomirov, G.M. (1999). A DFT quantum-chemical study of the structures and reactive sites of polymethylalumoxane. In: Kaminsky, W. (eds) Metalorganic Catalysts for Synthesis and Polymerization. Springer, Berlin, Heidelberg. https://doi.org/10.1007/978-3-642-60178-1_12
Download citation
DOI: https://doi.org/10.1007/978-3-642-60178-1_12
Publisher Name: Springer, Berlin, Heidelberg
Print ISBN: 978-3-642-64292-0
Online ISBN: 978-3-642-60178-1
eBook Packages: Springer Book Archive