TY - JOUR

T1 - Gas-phase Lewis acidity of perfluoroaryl derivatives of group 13 elements

AU - Timoshkin, Alexey Y.

AU - Frenking, Gernot

PY - 2008/2/11

Y1 - 2008/2/11

N2 - The gas-phase Lewis acidity of group 13 element aryl and perfluorinated aryl derivatives E(C6H5)3, E(C 6H4F)3, and E(C5F5) 3 (E = B, Al, Ga) toward different donor molecules (NH3, H2O, PH3, H-, CH3-, F-) has been theoretically studied at the RI-BP86/def2-TZVPP level of theory. The following order of the acceptor ability has been established: E(C6H5)3 ≈ E(C6H 4F)3 < E(C6F5)3 ≈ ECl3. The acceptor strengths of E(C6H5) 3 and E(C6H4F)3 are comparable to each other but much weaker compared to E(C6H5) 3, which has a similar acceptor strength to those of the corresponding trihalides ECl3. The acceptor ability of ER3 decreases in the order Al > Ga > B. In the gas phase, Al(C 6F5)3 is found to be a stronger Lewis acid than B(C6F5)3 toward all electron donors but H -. In contrast to AlCl3, which forms stable dimers, Al(C6F3)3 is monomelic and tiierefore has a much higher Lewis acid reactivity . The reactivity of perfluorinated derivatives E(C5F5)3 (E = B, Al, Ga) toward ammonolysis and hydrolysis processes and L2ZrMe2 (L = Cl, Cp, Cp*) as cocatalysts in olefin polymerization is also discussed.

AB - The gas-phase Lewis acidity of group 13 element aryl and perfluorinated aryl derivatives E(C6H5)3, E(C 6H4F)3, and E(C5F5) 3 (E = B, Al, Ga) toward different donor molecules (NH3, H2O, PH3, H-, CH3-, F-) has been theoretically studied at the RI-BP86/def2-TZVPP level of theory. The following order of the acceptor ability has been established: E(C6H5)3 ≈ E(C6H 4F)3 < E(C6F5)3 ≈ ECl3. The acceptor strengths of E(C6H5) 3 and E(C6H4F)3 are comparable to each other but much weaker compared to E(C6H5) 3, which has a similar acceptor strength to those of the corresponding trihalides ECl3. The acceptor ability of ER3 decreases in the order Al > Ga > B. In the gas phase, Al(C 6F5)3 is found to be a stronger Lewis acid than B(C6F5)3 toward all electron donors but H -. In contrast to AlCl3, which forms stable dimers, Al(C6F3)3 is monomelic and tiierefore has a much higher Lewis acid reactivity . The reactivity of perfluorinated derivatives E(C5F5)3 (E = B, Al, Ga) toward ammonolysis and hydrolysis processes and L2ZrMe2 (L = Cl, Cp, Cp*) as cocatalysts in olefin polymerization is also discussed.

UR - http://www.scopus.com/inward/record.url?scp=39649098242&partnerID=8YFLogxK

U2 - 10.1021/om700798t

DO - 10.1021/om700798t

M3 - Article

AN - SCOPUS:39649098242

VL - 27

SP - 371

EP - 380

JO - Organometallics

JF - Organometallics

SN - 0276-7333

IS - 3

ER -