III International Conference

PP-I-74DFT SIMULATION OF PROCESS OF KEY INTERMEDIATE FORMATION UPONCATALYTIC OLEFIN HYDROALUMINATIONPankratyev E.Y., Tyumkina T.V., Khalilov L.M., Parfenova L.V., Khursan S.L. 1 ,Dzhemilev U.M.Institute of Petrochemistry and Catalysis of RAS, Ufa, Russia1 Bashkir State University, Ufa, RussiaE-mail: lmk@anrb.ruWithin the mechanism investigation of olefin hydroalumination by HAlBu i 2 in thepresence of Cp 2 ZrCl 2 catalyst it was determined the structure of the key intermediate Zr,Alcomplexes1 by means of dynamic NMR spectroscopy [1]. It has been shown that complex 1is inactive in olefin hydroalumination.H AlBu 2Cp 2ZrHClHAlBu 21We performed quantum chemistry calculation of formation of complexe 1 by the DFTmethod - PBE/3z, program “Priroda 4.07”, Dimitri Laikov, Moscow State University, in thegas-phase at T=203.15 K (Scheme 1). It was found that formation of 1 occurs via the steps a-b-c. Summarized enthalpy of process is ΔH= -49.1 kcal/mol.Cp 2ZrHClAlBu i 2+HALBu i 2Cp 2ZrClHbCp 2ZrHHClaAlBui20 rCp 2ZrClH + ClAlBu i 2+HALBu i 2Cp 2ZrHScheme 1H AliBu H AliBu22ClCp 2ZrClcH AliBu H AliBu2 H22 1iia. Cp2 ZrCl2+ HAlBu2→ Cp2ZrCl2• HAlBu2ΔH0 r= -18.8 kcal/molCp2ii2ZrCl2• HAlBu2→ Cp2ZrClH+ ClAlBuΔ0 r=H 15.0 kcal/molb.Cp2ii2ZrHCl + HAlBu2→ Cp2ZrHCl• HAlBuΔ0 r=H -25.5 ккал/мольiiic. Cp ZrHCl • HAlBu + HAlBu → Cp ZrH ( HAlBu Cl ΔH= -19.8 ккал/моль2 22 22)2DFT energy profile has the local minimum and transition state, witch is shown in Fig. 1and Fig. 2.1390 r