Activation of SO₂ by N/Si⁺ and N/B Frustrated Lewis Pairs: Experimental and Theoretical Comparison with CO₂ Activation

Abstract

The guanidine 1,5,7‐triazabicyclo[4.4.0]dec‐5‐ene (TBD) and the substituted derivatives [TBD–SiR2]+ and TBD–BR2 reacted with SO2 to give different FLP–SO2 adducts. Molecular structures, elucidated by X‐ray diffraction, showed some structural similarities with the analogous CO2 adducts. Thermodynamic stabilities were both experimentally evidenced and computed through DFT calculations. The underlying parameters governing the relative stabilities of the different SO2 and CO2 adducts were discussed from a theoretical standpoint, with a focus on the influence of the Lewis acidic moiety.

Recent Advances in Group 14 and 15 Lewis Acids for Frustrated Lewis Pair Chemistry

“…Contrary to reaction with 9‐BBN and catBH, TBDSi i Pr 2 Cl and TBDSiPh 2 Cl performed better than TBDSiMe 2 Cl in the hydroboration of CO 2 with pinBH and the influence of the coordinating anion is also less pronounced here. In addition, these intramolecular FLPs also form stable adducts with SO 2 [42] . Although both the CO 2 and SO 2 complexes have very similar geometry the formation of SO 2 ‐adduct is found to be more favoured.…”

“…In addition, these intramolecular FLPs also form stable adducts with SO 2 . [42] Although both the CO 2 and SO 2 complexes have very similar geometry the formation of SO 2 -adduct is found to be more favoured. This observation is in line with the initial bent structure of SO 2 compared to linear CO 2 which helps SO 2 to accommodate the complex geometry easily.…”

Highly effective capture and subsequent catalytic transformation of low-concentration CO2 by superbasic guanidines

“…White solid (82%). 1 H NMR (400 MHz, CDCl 3 ) δ 7.64 (d,J = 8.6 Hz,2H),7.35 (d,J = 8.6 Hz,2H),6.36 (s,1H), 4.51 (m, J = 6.9 Hz, 1H), 4.30-4.00 (m, 1H), 1.42 (d, J = 7.0 Hz, 6H), 1.27 (d, J = 6.2 Hz, 6H). 13 C NMR (126 MHz, CDCl 3 ) δ 152.…”

Mechanism of Silyl Enol Ethers Hydrogenation Catalysed by Frustrated Lewis Pairs: A Theoretical Study

“…因为此方法不需要使用钌、铑、铱、钯等贵金属, 可以 有效避免金属残留和催化剂失活等问题, 目前已引起各 国科研工作者极大的研究兴趣 [19] . 截止目前, FLPs 已作 为催化剂被应用于亚胺、烯胺、烯烃、多芳香烃、炔烃、 酮和醛等不饱和化合物的氢化反应 [12,[20][21][22][23][24][25][26][27][28][29][30] ; 此外, 有报 道显示: FLPs 还能活化 N 2 、CO 2 、SO 2 、NO、CO、N 2 O 等小分子 [31][32][33][34][35] , 进一步扩展了 FLPs 化学的范畴.…”