Abstract
We have analyzed the computational results for several elementary reactions of the ethylene polymerization process catalyzed by an alternative (to the existing metallocene catalysts) “non-cyclopentadienyl” catalysts such as diimine-M(II) (where M = Ni and Pd) and chelating bridged Ti- and Zr-complexes. The obtained data have been compared with those for the existing zirconocene-based catalysts. In general, it was shown that: (i) the resting stage of the process is a metal-olefin-alkyl complex, the olefin coordination energy of which is a few kcal/mol larger for diimine-M(II) systems than zirconocene or dialkoxide systems; (ii) the rate-determining barrier is a migratory insertion barrier calculated from the metal-olefin-alkyl complex, which is found to be a few kcal/mol larger for the diimine-M(II) system compared to the Cp2ZrCH +3 catalyst. The presence of certain flexible bridging ligands X in the Ti-alkoxide complex, [Y(Ph)X(Ph)Y]TiCH +3 , which are capable of donating electron density to the cationic metal center at various stages during the reaction makes this barrier a few kcal/mol smaller for the dialkoxide than the Cp2ZrCH +3 catalyst. It was shown that an increase in the metal-bridge interaction decreases the migratory insertion barrier and, consequently, increases the catalytic activity of these complexes. Although the diimine-M(II) catalysts are less active than zirconocene-based ones, the microstructure of the polymers produced by the former catalyst, which is found to be a function of temperature, ethylene, steric bulkiness of the auxiliary ligands, and transition metal center, makes them attractive for practice. We also have studied the mechanisms of several chain termination/transfer reactions, as well as the role of steric effects in the studied elementary reactions. We have clearly demonstrated tremendous possibilities of the computational chemistry in solving complex problems of the homogenous catalyst, and its high capability of predicting new and more active catalysts for different commercially important processes including olefin polymerization reactions.
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References
K. Ziegler, E. Holzkamp, H. Breil and H. Martin, Angew. Chem. 67 (1955) 541.
K. Ziegler, Angew. Chem. 76 (1964) 545.
G. Natta and P. Corradini, Atti Accad. naz. Lincei Mem. Cl. Sci. Fis. Mat. Nat. Sez. II 5 (1955) 73.
G. Natta, Angew. Chem. 68 (1956) 393; 76 (1964) 553.
R.B. Seymour and T. Cheng, eds., History of Polyolefins (Reidel, Dordrecht, 1986).
J.J.J. Eisch, Chem. Educ. 60 (1983) 1009.
J. Boor, Ziegler-Natta Catalysts and Polymerizations (Academic Press, New York, 1979).
D.S. Breslow and N.R. Newburg, J. Am. Chem. Soc. 79 (1957) 5072.
D.S. Breslow and N.R. Newburg, J. Am. Chem. Soc. 81 (1959) 81.
W.P. Long, J. Am. Chem. Soc. 81 (1959) 5312.
W.P. Long and D.S. Breslow, J. Am. Chem. Soc. 82 (1960) 1953.
G. Natta, P. Pino, G. Mazanti and R. Lanzo, Chim. Ind. (Milan) 79 (1957) 5072.
K.H. Reichert and K.R. Meyer, Macromol. Chem. 169 (1973) 163.
H. Sinn and W. Kaminsky, Adv. Organomet. Chem. 18 (1980) 99.
J.A. Ewen, J. Am. Chem. Soc. 106 (1984) 6355.
F.R.W.P. Wild, M. Wasivcionek, G. Huttner and H.H. Brintzinger, J. Organomet. Chem. 288 (1985) 63.
W. Kaminsky, K. Kulper, H.H. Brintzinger and F.R.W.P. Wild, Angew. Chem., Int. Ed. Engl. 24 (1985) 507.
J.A. Ewen, R.L. Jones, A. Razavi and J.D. Ferrara, J. Am. Chem. Soc. 110 (1988) 6255.
R.F. Jordan, Chem. Educ. 65 (1988) 285.
Y.W. Alelynuas, R.F. Jordan, S.F. Echols, S.L. Borkowsky and P.K. Bradley, Organometallics 10 (1991) 1406.
P.G. Gassman and M.R. Callstrom, J. Am. Chem. Soc. 109 (1987) 7875.
R.F. Jordan, C.S. Bajgur, R. Willet and B. Scott, J. Am. Chem. Soc. 108 (1986) 7410.
C.F. Jordan, R.E. La Pointe, C.S. Bajgur, S.F. Echols and R. Willet, J. Am. Chem. Soc. 109 (1987) 4111.
J. Huang and G.L. Rempel, Prog. Polymer Sci. 20 (1995) 459.
H.H. Brintzinger, D. Fischer, R. Mulhaupt, B. Rieger and R.M. Waymouth, Angew. Chem., Int. Ed. Engl. 34 (1995) 1143.
P.C. Mohring and N.J. Coville, J. Organomet. Chem. 479 (1994) 1.
N. Schneider, M.E. Huttenloch, U. Stehling, R. Kirsten, F. Schaper and H.H. Brintzinger, Organometallics 16 (1997) 3413.
M.K. Leclerc and H.H. Brintzinger, J. Am. Chem. Soc. 117 (1995) 1651.
V. Busico, L. Caporaso, R. Cipullo, L. Landriani, G. Angelini, A. Margonelli and A.L. Segre, J. Am. Chem. Soc. 118 (1996) 2105.
G.C. Bazan, G. Rodroguez, A.J. Ashe III, S. Al-Ahmad and C. Muller, J. Am. Chem. Soc. 118 (1996) 2291.
N.G. Alameddin, M.F. Ryan, J.R. Eyler, A.R. Siedle and D.E. Richardson, Organometallics 14 (1995) 5005.
G.W. Coates and R.M. Waymouth, Science 267 (1995) 217.
X. Yang, C.L. Stern and T.J. Marks, J. Am. Chem. Soc. 116 (1994) 10015.
E.B. Coughlin and J.E. Bercaw, J. Am. Chem. Soc. 114 (1992) 7606.
D.J. Crowther, N.C. Baenziger and R.F. Jordan, J. Am. Chem. Soc. 113 (1991) 1455.
C. Janiak, U. Versteeg, K.C.H. Lange, R. Weimann and E. Hahn, J. Organomet. Chem. 501 (1995) 219.
C. Janiak, K.C.H. Lange and P. Marquardt, Macromol. Rapid Commun. 16 (1995) 643.
G. Rodriguez and G.C. Bazan, J. Am. Chem. Soc. 119 (1997) 343 and references therein.
M. Bochmann and S.J. Lancaster, J. Organomet. Chem. 434 (1992) C1.
M.K. Leclerc and H.H. Brintzinger, J. Am. Chem. Soc. 118 (1996) 9024.
P.A. Deck, C.L. Beswick and T.J. Marks, J. Am. Chem. Soc. 120 (1998) 7875 and references therein.
R. Fusco, L. Longo, F. Masi and F. Garbassi, Macromol. 30 (1997) 7673 and references therein.
N.S. Barta, B.A. Kirk and J.A. Stille, J. Am. Chem. Soc. 116 (1994) 8912.
X. Yang, C.L. Stern and T.J. Marks, J. Am. Chem. Soc. 113 (1991) 3613.
J.C.W. Chein, W.-M. Tsai and M.D. Rausch, J. Am. Chem. Soc. 113 (1991) 8570.
L. Jia, X. Yang, A.M. Seyam, I.D.L. Albert, P.-F. Fu, S. Yang and T.J. Marks, J. Am. Chem. Soc. 118 (1996) 7900 and references therein.
T. Yoshida, N. Koga and K. Morokuma, Organometallics 14 (1995) 746.
T. Yoshida, N. Koga and K. Morokuma, Organometallics 15 (1996) 766.
I. Hyla-Kryspin, S. Niu and R. Gleiter, Organometallics 14 (1995) 964.
N. Koga and K. Morokuma, J. Am. Chem. Soc. 110 (1988) 108.
J.C.W. Lohrenz, T.K. Woo and T. Ziegler, J. Am. Chem. Soc. 117 (1995) 108.
T.K. Woo, L. Fan and T. Ziegler, Organometallics 13 (1994) 2252.
L. Fan, D. Harrison, L. Deng, T.K. Woo, D. Swerhone and T. Ziegler, Can. J. Chem. 73 (1995) 989.
L. Fan, D. Harrison, T.K. Woo and T. Ziegler, Organometallics 14 (1995) 2018.
J.C.W. Lohrenz, T.K. Woo, L. Fan and T. Ziegler, J. Organomet. Chem. 497 (1995) 91.
J.C.W. Lohrenz, T.K. Woo and T. Ziegler, J. Am. Chem. Soc. 117 (1995) 12793.
H. Weiss, M. Ehrig and R. Ahlrichs, J. Am. Chem. Soc. 116 (1994) 4919.
L. Fan, A. Krzywicki, A. Somogyvari and T. Ziegler, Inorg. Chem. 35 (1996) 4003.
L. Fan, A. Krzywicki, A. Somogyvari and T. Ziegler, Stud. Surf. Sci. Catal. 100 (1996) 507.
P.K. Das, D.W. Dockter, D.R. Fahey, D.E. Lauffer, G.D. Hawkins, J. Li, T. Zhu, C.J. Cramer, D.G. Truhlar, S. Dapprich, R.D.J. Froese, M.C. Holthausen, Z. Liu, K. Mogi, S. Vyboishchikov, D.G. Musaev and K. Morokuma, in: Transition State Modeling for Catalysis, eds. D.G. Truhlar and K. Morokuma, ASC Series, Washington, 1998.
P. Cossee, J. Catal. 3 (1964) 80.
E.J. Arlman, J. Catal. 3 (1964) 89.
E.J. Arlman and P. Cossee, J. Catal. 3 (1964) 99.
W. Kaminsky and R. Steiger, Polyhedron 109 (1998) 7875.
P. Corradini and G. Guerra, Prog. Polym. Sci. 16 (1991) 239.
M. Ystenes, Macromol. Chem., Macromol. Symp. 66 (1993) 71.
M. Brookhart, M.L.H. Green, J. Organomet. Chem. 250 (1983) 395.
D.G. Musaev, R.D.J. Froese, M. Svensson and K. Morokuma, J. Am. Chem. Soc. 119 (1997) 367.
D.G. Musaev, M. Svensson, K. Morokuma, S. Str¨omberg, K. Zetterberg and P.E.M. Siegbahn, Organometallics 16 (1997) 1933.
D.G. Musaev, R.D.J. Froese and K. Morokuma, New J. Chem. 21 (1997) 1269.
R.D.J. Froese, D.G. Musaev and K. Morokuma, J. Am. Chem. Soc., submitted.
D.G. Musaev, R.D.J. Froese, M. Svensson and K. Morokuma, Organometallics 17 (1998) 1850.
L. Deng, P. Margl and T. Ziegler, J. Am. Chem. Soc. 119 (1997) 1094.
L. Deng, T.K. Woo, L. Cavallo, P. Margl and T. Ziegler, J. Am. Chem. Soc. 119 (1997) 6177.
R.D.J. Froese, D.G. Musaev, T. Matsubara and K. Morokuma, J. Am. Chem. Soc. 119 (1997) 7190.
R.D.J. Froese, D.G. Musaev and K. Morokuma, Organometallics, in press.
G.J.P. Britovsek, V.C. Gibson, B.S. Kimberley, P.J. Maddox, S.J. McTavish, G.A. Solan, A.J.P. White and D.J. Williams, Chem. Commun. (1998) 849.
B.L. Small and M. Brookhart, J. Am. Chem. Soc. 120 (1998) 7143.
J.D. Scollard, D.H. McConville, N.C. Payne and J.J. Vittal, Macromol. 29 (1996) 5241.
J.C. Flores, J.C.W. Chien and M.D. Rausch, Organometallics 14 (1995) 1827.
D. Herskovics-Korine and M.S. Eisen, J. Organomet. Chem. 503 (1995) 307.
B.-J. Deelman, M.F. Lappert, H.-K. Lee, T.C.W. Mak, W.-P. Leung and P.-R. Wei, Organometallics 116 (1997) 1247.
B.-J. Deelman, P.B. Hitchcock, M.F. Lappert, H.-K. Lee and W.-P. Leung, J. Organomet. Chem. 513 (1996) 281.
L.K. Johnson, C.M. Killian and M. Brookhart, J. Am. Chem. Soc. 117 (1995) 6414.
L.K. Johnson, S. Mecking and M. Brookhart, J. Am. Chem. Soc. 118 (1996) 267.
W. Keim, Angew. Chem., Int. Ed. Engl. 29 (1990) 235.
R. Abecywickrema, M.A. Bennett, K.J. Cavell, M. Kony, A.F. Masters and A.G. Webb, J. Chem. Soc., Dalton Trans. (1993) 59.
S.J. Brown and A.F. Masters, J. Organomet. Chem. 367 (1989) 371.
A.D. Becke, Phys. Rev. A 38 (1988) 3098.
C. Lee, W. Yang and R.G. Parr, Phys. Rev. B 37 (1988) 785.
A.D. Becke, J. Chem. Phys. 98 (1993) 5648.
M.J. Frisch, G.W. Trucks, H.B. Schlegel, P.M.W. Gill, B.G. Johnson, M.A. Robb, J.R. Cheeseman, T.A. Keith, J.A. Petersson, J.A. Montgomery, K. Raghavachari, M.A. Al-Laham, V.G. Zakrzewski, J.V. Ortiz, J.B. Foresman, J. Cioslowski, B.B. Stefanov, A. Nanayakkara, M. Challacombe, C.Y. Peng, P.Y. Ayala, W. Chen, M.W. Wong, J.L. Andres, E.S. Replogle, R. Gomperts, R.L. Martin, D.J. Fox, J.S. Binkley, D.J. DeFrees, J. Baker, J.J.P. Stewart, M. Head-Gordon, C. Gonzales and J.A. Pople, GAUSSIAN94 (Gaussian Inc., Pittsburgh, PA, 1995).
Q. Cui, D.G. Musaev, M. Svensson and K. Morokuma, J. Phys. Chem. 100 (1996) 10936.
F. Maseras and K. Morokuma, J. Comp. Chem. 16 (1995) 1170.
T. Matsubara, F. Maseras, N. Koga and K. Morokuma, J. Phys. Chem. 100 (1996) 2573.
T. Matsubara, S. Sieber and K. Morokuma, Int. J. Quantum Chem. 60 (1996) 1101.
R.D.J. Froese and K. Morokuma, Chem. Phys. Lett. 263 (1996) 393.
MM3(92): Quantum Chemistry Program Exchange, Indiana University, 1992.
A. Aped and N.L. Allinger, J. Am. Chem. Soc. 114 (1992) 1.
A.K. Rappe, C.J. Casewit, K.S. Colwell, W.A. Goddard III and W.M. Skiff, J. Am. Chem. Soc. 114 (1992) 10024.
M. Kakugo, T. Miyatake and K. Mizunuma, Chem. Express 2 (1987) 445.
T. Miyatake, K. Mizunuma, Y. Seki and M. Kakugo, Makromol. Chem., Rapid Commun. 10 (1989) 349.
T. Miyatake, K. Mizunuma and M. Kakugo, Makromol. Chem., Macromol. Symp. 66 (1983) 203.
S. Fokken, T.P. Spaniol, H.-C. Kang, W. Massa and J. Okuda, Organometallics 15 (1996) 5069.
A. van der Linden, C.J. Schaverien, N. Meijboom, C. Ganter and A.G. Orpen, J. Am. Chem. Soc. 117 (1995) 3008.
C.J. Schaverien, A. van der Linden and A.G. Orpen, Am. Chem. Soc., Polym. Div., Polymer Prepr. 35 (1994) 672.
R. Baumann, W.M. Davis and R.R. Schrock, J. Am. Chem. Soc. 119 (1997) 3830.
R. Baumann and R.R. Schrock, J. Am. Chem. Soc. (1998) in press.
F. Guerin, D.H. McConville and J.J. Vittal, Organometallics 14 (1995) 3154.
H.C.S. Clark, F.G.N. Cloke, P.B. Hitchcock, J.B. Love and A.P. Wainwright, J. Organomet. Chem. 501 (1995) 333.
F.G.N. Cloke, P.B. Hitchcock and J.B. Love, J. Chem. Soc., Dalton Trans. (1995) 25.
J.D. Scollard, D.H. McConville and J.J. Vittal, Organometallics 14 (1995) 5478.
T.H. Warren, R.R. Schrock and W.M. Davis, Organometallics 16 (1996) 562.
D.G. Musaev and K. Morokuma, in:Adv.Chem.Phys., Vol. XCV, eds. I. Prigogine and A. Rice (Wiley, New York, 1996) pp. 61–128.
[115] W. Chen and M.S. Gordon, J. Phys. Chem. 100 (1996) 14316.
W. Chen and M.S. Gordon, J. Chem. Phys. 105 (1996) 11081.
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Musaev, D.G., Morokuma, K. Theoretical studies of the mechanism of ethylene polymerization reaction catalyzed by diimine-M(II) (M = Ni, Pd and Pt) and Ti- and Zr-chelating alkoxides. Topics in Catalysis 7, 107–123 (1999). https://doi.org/10.1023/A:1019147313488
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DOI: https://doi.org/10.1023/A:1019147313488