from first principles PP-I-1

Computer Construction of Kinetic Model of Detailed OlefinHydroalumination MechanismKoledina K.F. 1 , Gubaidullin I.M. 2 , Novichkova A.V. 21 Bashkir State University, Ufa, RussiaPP-I-62 Institute of Petrochemistry and Catalysis, Russian Academy of Sciences, Ufa, Russiasabitovakamila@rambler.ruInvestigation of the hydroalumination reaction of olefins with organoaluminum compounds(OACs) such as diisobutylaluminum hydride HAlBu i 2 (DIBAH), diisobutylaluminum chlorideClAlBu i 2 (DIBAC), and triisobutylaluminum AlBu i 3 (TIBA) has great significance in bothsynthetic chemistry and fundamental science. Several mechanisms of olefin hydroaluminationhave been proposed and include mechanism of the overall reaction and mechanisms for theselected separate reactions between each OAC and olefin in the form of final equations [1],the first and second specification of the selected reactions [2, 3] and the detailed generalreaction mechanism with elementary stages.k 13= 0,13Е -02 E 13= 31ClAlBu i Cp Cp2Cp 2ZrCl 2Cp 2ZrClBuCl H Cl- Cl 2AlBuiii(1)2 (3)Bu 2Al Zr Zr AlBu(14)2H H HXAlBu i 2k -1 3= 0,27Е -06 k 14= 0,3E Cp Cpi-1 3= 1 E k H AlBu(6)2= 10,4 k 6= 2,814= 12,62HAlBu i 2C 4H(2)8 (13)E 2= 5,8 E 6= 12,3Cp 2Zr H Clk i-17= 0,04 k 17= 0,24Е -05H AlBuE 2-1 7= 10,1 E 17= 13,6k -1= 97,3 k 1= 4,9HAlBu i (7)2k 8=412,6E -1= 7 E 1= 4,5CpE 8= 10,6k 3= 453,9ClClAlBu i 2Cl Zr AlBuiE 3= 7H2- C l 2AlBui2CpCp- C Cl4H 8i(5)H Zr AlBuClAlBu i H2k2 k 7= 3,712=0,012CECp12= 26E R7= 8(15) (8)k -7=757,5k 9=314ClE -7= 11,1 HAlBu i 2E 9= 0,8 Cp 2Zr(9)RRk+15= 0,4k 10=1071,9k 11=1Bu 2AlRHAlBu i E 10= 7E 15= 26,72kClAlBu i E 16= 106,111= 6,62+ClAlBu i E216= 18,2Cp 2ZrHClk- 16= 0,27Е -06E -1 6= 19Cl 2AlBui2(12)ClBuAlRFigure 1. Generalized kinetic model of the catalytic olefin hydroalumination reaction.It follows from Figure 1, that the dimerization reaction of complex (15) (E = 7,02 kcal/mole)and the interaction between (15) and a DIBAH molecule (E = 7 kcal/mole) are almost equallyprobable. But in hydroalumination of olefins with DIBAC diisobutylaluminum hydride is notinitial substance, it is formed during the reaction in small quantities. Therefore, dimerizationof (15) is more probable resulting in the formation of complex (6). Taking into account the121