Technische Universität Berlin, Department of Chemistry, Metalorganics and Inorganic Materials, Sekr. C2, Strasse des 17. Juni 135, 10623 Berlin, Germany.
Chem Commun (Camb). 2013 Jun 21;49(49):5595-7. doi: 10.1039/c3cc41965g.
The facile synthesis of the first stable selenosilanoic acid-base adduct LSi(=Se)OH(dmap) 3 (L = CH[C(Me)NAr]2, Ar = 2,6-iPr2C6H3, dmap = 4-dimethylaminopyridine), the heavier analogue of the thiosilanoic acid adduct LSi(=S)OH(dmap) 1, is reported. Both adducts 1 and 3 react readily with MesCu (Mes = 2,4,6-trimethylphenyl) to form the novel dimeric Cu(I) complexes [LSi(=E)OCu]2 (4: E = S; 5: E = Se) with unprecedented intermolecular Si=E → Cu-O-Si coordination modes. The latter are efficient pre-catalysts for the Cu(I)-mediated aziridination of styrene with PhI=N(Ts) (Ts = tosyl).
报告了首例稳定硒硅烷酸碱加合物 LSi(=Se)OH(dmap)3（L = CH[C(Me)NAr]2，Ar = 2,6-iPr2C6H3，dmap = 4-二甲基氨基吡啶）的简便合成，它是硫硅烷酸加合物 LSi(=S)OH(dmap)1 的较重类似物。这两种加合物 1 和 3 都很容易与 MesCu（Mes = 2,4,6-三甲基苯基）反应，形成新型二聚 Cu(I)配合物[LSi(=E)OCu]2（4：E = S；5：E = Se），具有前所未有的分子间 Si=E → Cu-O-Si 配位模式。后者是在 PhI=N(Ts)（Ts = 对甲苯磺酰基）存在下通过 Cu(I)介导的苯乙烯氮丙啶化的有效预催化剂。
