作者:André Hermannsdorfer、Matthias Driess
DOI:10.1002/anie.202011696
日期:2020.12.14
coordination and to the expense of reduced fluoride‐ion affinities, but a significant level of Lewis superacidity is nonetheless retained as verified by theory and experiment. The complexes activate C(sp3)−F bonds, as showcased by stoichiometric fluoride abstraction from 1‐fluoroadamantane (AdF) and the catalytic hydrodefluorination of AdF. The formation of the crystalline adducts [2(F)]+ and [5(H)]2+ documents
R 2 Si 2+和RSi 3+ (R=H,有机基团)类型的分子硅聚阳离子是难以捉摸的路易斯超强酸,目前在凝聚相中未知。在这里,我们报道了一系列可分离的三联吡啶稳定的R 2 Si 2+和RSi 3+配合物的合成,[R 2 Si(terpy)] 2+ (R=Ph 1 2+ ; R 2 =C 12 H 8 2 2+ 、(CH 2 ) 3 3 2+ ) 和 [RSi(terpy)] 3+ (R=Ph 4 3+ 、环己基5 3+ 、间二甲苯基6 3+ ),为其三氟甲磺酸盐形式。后者的稳定是通过更高的配位和降低氟离子亲和力来实现的,但经理论和实验验证,仍然保留了显着水平的路易斯超酸性。从 1-氟金刚烷 (AdF) 中按化学计量提取氟化物以及 AdF 的催化加氢脱氟反应表明,该配合物可激活 C(sp 3 )−F 键。结晶加合物[ 2 (F)] +和[ 5 (H)] 2+的形成特别证明了对氟化物和氢化物供体的高反应性。