On Silylated Oxonium and Sulfonium Ions and Their Interaction with Weakly Coordinating Borate Anions.,Chemistry - A European Journal

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On Silylated Oxonium and Sulfonium Ions and Their Interaction with Weakly Coordinating Borate Anions.
Chemistry - A European Journal ( IF 3.9 ) Pub Date : 2020-01-24 , DOI: 10.1002/chem.201904403
Kevin Bläsing ₁ , Rene Labbow ₁ , Dirk Michalik _{1,

2} , Fabian Reiß _{1,

2} , Axel Schulz _{1,

2} , Alexander Villinger ₁ , Svenja Walker ₁

Affiliation

Attempts have been made to prepare salts with the labile tris(trimethylsilyl)chalconium ions, [(Me3 Si)3 E]+ (E=O, S), by reacting [Me3 Si-H-SiMe3 ][B(C6 F5 )4 ] and Me3 Si[CB] (CB- =carborate=[CHB11 H5 Cl6 ]- , [CHB11 Cl11 ]- ) with Me3 Si-E-SiMe3 . In the reaction of Me3 Si-O-SiMe3 with [Me3 Si-H-SiMe3 ][B(C6 F5 )4 ], a ligand exchange was observed in the [Me3 Si-H-SiMe3 ]+ cation leading to the surprising formation of the persilylated [(Me3 Si)2 (Me2 (H)Si)O]+ oxonium ion in a formal [Me2 (H)Si]+ instead of the desired [Me3 Si]+ transfer reaction. In contrast, the expected homoleptic persilylated [(Me3 Si)3 S]+ ion was formed and isolated as [B(C6 F5 )4 ]- and [CB]- salt, when Me3 Si-S-SiMe3 was treated with either [Me3 Si-H-SiMe3 ][B(C6 F5 )4 ] or Me3 Si[CB]. However, the addition of Me3 Si[CB] to Me3 Si-O-SiMe3 unexpectedly led to the release of Me4 Si with simultaneous formation of a cyclic dioxonium dication of the type [Me3 Si-μO-SiMe2 ]2 [CB]2 in an anion-mediated reaction. DFT studies on structure, bonding and thermodynamics of the [(Me3 Si)3 E]+ and [(Me3 Si)2 (Me2 (H)Si)E]+ ion formation are presented as well as mechanistic investigations on the template-driven transformation of the [(Me3 Si)3 E]+ ion into a cyclic dichalconium dication [Me3 Si-μE-SiMe2 ]2 2+ .

中文翻译：

关于甲硅烷基化氧鎓和锍离子及其与弱配位硼酸盐阴离子的相互作用。

已尝试通过 [Me3 Si-H-SiMe3 ][B(C6 F5 ) 反应，用不稳定的三（三甲基甲硅烷基）查尔离子 [(Me3 Si)3 E]+ (E=O, S) 制备盐。 4]和Me3 Si[CB]（CB-=碳酸盐=[CHB11 H5 Cl6]-，[CHB11 Cl11]-）与Me3 Si-E-SiMe3。在 Me3 Si-O-SiMe3 与 [Me3 Si-H-SiMe3 ][B(C6 F5 )4 ] 的反应中，在 [Me3 Si-H-SiMe3 ]+ 阳离子中观察到配体交换，导致令人惊讶的形成全甲硅烷基化的 [(Me3 Si)2 (Me2 (H)Si)O]+ 氧鎓离子在正式的 [Me2 (H)Si]+ 中代替所需的 [Me3 Si]+ 转移反应。相比之下，当 Me3 Si-S-SiMe3 用 [ Me3 Si-H-SiMe3][B(C6 F5)4]或Me3 Si[CB]。然而，将 Me3 Si[CB] 添加到 Me3 Si-O-SiMe3 中意外地导致 Me4 Si 的释放，同时形成 [Me3 Si-μO-SiMe2 ]2 [CB]2 类型的环状二氧鎓阳离子。阴离子介导的反应。介绍了 [(Me3 Si)3 E]+ 和 [(Me3 Si)2 (Me2 (H)Si)E]+ 离子形成的结构、成键和热力学的 DFT 研究，以及模板驱动的机理研究[(Me3 Si)3 E]+ 离子转化为环状二查尔阳离子 [Me3 Si-μE-SiMe2 ]2 2+ 。

更新日期：2020-01-24

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