TY - JOUR

T1 - Interaction of perfluorinated group 13 Lewis acids with diatomic halogens and interhalogens: computational and experimental study

AU - Помогаева, Анна Владимировна

AU - Лисовенко, Анна Сергеевна

AU - Казаков, Игорь Владимирович

AU - Завгородний, Артем Сергеевич

AU - Глухович, Екатерина Вячеславовна

AU - Елисеев, Алексей Дмитриевич

AU - Афанасьев, Алексей Юрьевич

AU - Шарапова, Динара Азатовна

AU - Куликова, Яна Игоревна

AU - Тимошкин, Алексей Юрьевич

PY - 2024/11/14

Y1 - 2024/11/14

N2 - Interaction of perfluorinated group 13 element Lewis acids E(C6F5)3 (E=B, Al, Ga, In) and Al{OC(CF3)3}3 with diatomic halogens and interhalogens was studied computationally. Boron-containing derivative is predicted to form weak complexes with halogens and to be thermodynamically stable with respect to iodination, while its heavier derivatives form stronger complexes that are unstable with respect to E C bond oxidation. The reactivity of E(C6F5)3 with iodine and iodine monochloride and Al{OCR3}3 (R=CF3, C6F5) with iodine was explored experimentally. Experimental data confirm that B(C6F5)3 does not react with ICl at room temperature and with molecular iodine in temperature range 233–350 K. Heavier group 13 element derivatives E(C6F5)3 upon reaction with I2 and ICl undergo oxidation processes with C6F5I evolution. Both Al{OC(CF3)3}3*C6H5F and Al{OC(C6F5)3}3 do not form stable complexes with molecular iodine.

AB - Interaction of perfluorinated group 13 element Lewis acids E(C6F5)3 (E=B, Al, Ga, In) and Al{OC(CF3)3}3 with diatomic halogens and interhalogens was studied computationally. Boron-containing derivative is predicted to form weak complexes with halogens and to be thermodynamically stable with respect to iodination, while its heavier derivatives form stronger complexes that are unstable with respect to E C bond oxidation. The reactivity of E(C6F5)3 with iodine and iodine monochloride and Al{OCR3}3 (R=CF3, C6F5) with iodine was explored experimentally. Experimental data confirm that B(C6F5)3 does not react with ICl at room temperature and with molecular iodine in temperature range 233–350 K. Heavier group 13 element derivatives E(C6F5)3 upon reaction with I2 and ICl undergo oxidation processes with C6F5I evolution. Both Al{OC(CF3)3}3*C6H5F and Al{OC(C6F5)3}3 do not form stable complexes with molecular iodine.

KW - Halogens

KW - Perfluorinated Lewis acids

KW - Complexes

KW - Reactivity

KW - Quantum chemical studies

UR - https://chemistry-europe.onlinelibrary.wiley.com/doi/10.1002/ejic.202400620

U2 - 10.1002/ejic.202400620

DO - 10.1002/ejic.202400620

M3 - Article

VL - 28

JO - Berichte der deutschen chemischen Gesellschaft

JF - Berichte der deutschen chemischen Gesellschaft

SN - 0365-9496

M1 - e202400620

ER -