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Anion Chelation via Double Chalcogen Bonding: The Case of a Bis-telluronium Dication and Its Application in Electrophilic Catalysis via Metal–Chloride Bond Activation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-06-04 , DOI: 10.1021/jacs.1c04482 Benyu Zhou 1 , François P Gabbaï 1
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2021-06-04 , DOI: 10.1021/jacs.1c04482 Benyu Zhou 1 , François P Gabbaï 1
Affiliation
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Telluronium cations have long been known to engage their counteranions via secondary interactions. Yet, this property has rarely been exploited for anion binding. Motivated by such an application, we have now synthesized a bis-telluronium dication ([3]2+) that was obtained as a tetrafluoroborate salt by reaction of 2,7-di-tert-butyl-9,9-dimethylxanthene-4,5-diboronic acid with phenoxatellurine difluoride and BF3·OEt2. As confirmed by the formation of Te-(μ-BF4)-Te bridges in the structure of [3][BF4]2, [3]2+ functions as a bidentate Lewis acid toward anions. [3][BF4]2 has also been converted into the more exposed [3][BArF24]2 ([BArF24]− = [B(3,5-(CF3)2C6H3)4]−). The latter, which readily ionizes Ph3CCl, displays a chloride anion binding constant that exceeds that of a monofunctional model compound by almost 4 orders of magnitude. The unique properties of this new bis-telluronium dication are further highlighted by its ability to activate Ph3PAuCl and cis-(Ph3P)2PtCl2, leading to catalytic systems highly active in the cycloisomerization of propargylamide or enyne substrates.
中文翻译：
通过双硫属元素键合进行阴离子螯合：双碲二阳离子及其在金属-氯化物键活化亲电催化中的应用
人们早就知道碲阳离子通过二次相互作用与它们的反阴离子结合。然而，这种特性很少被用于阴离子结合。受此类应用的启发，我们现在合成了一种双碲二阳离子 ([ 3 ] 2+ )，它是通过 2,7-二叔丁基-9,9-二甲基氧杂蒽-4的反应获得的四氟硼酸盐， 5-二硼酸与二氟化苯氧苯胺和BF 3 ·OEt 2。[ 3 ][BF 4 ] 2 , [ 3 ] 2+结构中Te-(μ-BF 4 )-Te桥的形成证实了这一点作为对阴离子的双齿路易斯酸。[ 3 ][BF 4 ] 2也被转换成更暴露的[ 3 ][BArF 24 ] 2 ([BArF 24 ] − = [B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 ] - )。后者易于电离 Ph 3 CCl，其氯阴离子结合常数比单功能模型化合物高出近 4 个数量级。这种新的双碲二阳离子的独特性质因其激活 Ph 3 的能力而进一步突出PAuCl和顺式-(Ph 3 P) 2 PtCl 2，导致催化体系在炔丙酰胺或烯炔底物的环异构化中具有高活性。
更新日期：2021-06-17
中文翻译：
通过双硫属元素键合进行阴离子螯合：双碲二阳离子及其在金属-氯化物键活化亲电催化中的应用
人们早就知道碲阳离子通过二次相互作用与它们的反阴离子结合。然而，这种特性很少被用于阴离子结合。受此类应用的启发，我们现在合成了一种双碲二阳离子 ([ 3 ] 2+ )，它是通过 2,7-二叔丁基-9,9-二甲基氧杂蒽-4的反应获得的四氟硼酸盐， 5-二硼酸与二氟化苯氧苯胺和BF 3 ·OEt 2。[ 3 ][BF 4 ] 2 , [ 3 ] 2+结构中Te-(μ-BF 4 )-Te桥的形成证实了这一点作为对阴离子的双齿路易斯酸。[ 3 ][BF 4 ] 2也被转换成更暴露的[ 3 ][BArF 24 ] 2 ([BArF 24 ] − = [B(3,5-(CF 3 ) 2 C 6 H 3 ) 4 ] - )。后者易于电离 Ph 3 CCl，其氯阴离子结合常数比单功能模型化合物高出近 4 个数量级。这种新的双碲二阳离子的独特性质因其激活 Ph 3 的能力而进一步突出PAuCl和顺式-(Ph 3 P) 2 PtCl 2，导致催化体系在炔丙酰胺或烯炔底物的环异构化中具有高活性。
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