Université de Toulouse, UPS, LHFA, and CNRS, LHFA UMR 5069, 118 Route de Narbonne, 31062 Toulouse (France).
Angew Chem Int Ed Engl. 2015 Jan 12;54(3):805-8. doi: 10.1002/anie.201406283. Epub 2014 Nov 27.
The efficiency of the deprotonated aryl bis-sulfone 2,6-{(p-tolyl)SO2}2C6H3 as an O,C,O-coordinating pincer-type ligand was described. The bis-sulfone precursor was synthesized using a straightforward palladium-catalyzed cross-coupling reaction. As a result of directed ortho metalation (DoM) through sulfonyl groups, a selective lithiation of the aryl group was achieved and the corresponding carbanion was isolated and its structure determined by single-crystal X-ray diffraction analysis. A heteroleptic tin(II) complex has been prepared by a nucleophilic substitution reaction. Crystallographic analysis and DFT calculations indicate that the bis-sulfonyl moiety acts as a new O,C,O-coordinating pincer-type ligand with intramolecular S=O coordination to a tin(II) center. The cis form with the two nonbonded oxygen atoms of the sulfonyl groups on the same side is preferentially obtained.
描述了去质子芳基双砜2,6-{(对甲苯基)SO2}2C6H3作为 O,C,O-配位的钳式配体的效率。双砜前体是通过简单的钯催化交叉偶联反应合成的。由于通过砜基进行定向邻位金属化（DoM），实现了芳基的选择性锂化，并通过单晶 X 射线衍射分析分离和确定了相应的碳负离子的结构。通过亲核取代反应制备了杂化锡（II）配合物。晶体结构分析和 DFT 计算表明，双砜基部分作为一种新型的 O,C,O-配位的钳式配体，通过分子内 S=O 与锡（II）中心配位。优先得到具有两个非键合的砜基氧原子在同一侧的顺式形式。
