Reductive Cleavage of the CO Molecule by a Reactive Vicinal Frustrated PH/BH Lewis Pair.,Journal of the American Chemical Society

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Reductive Cleavage of the CO Molecule by a Reactive Vicinal Frustrated PH/BH Lewis Pair.
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2020-09-16 , DOI: 10.1021/jacs.0c07161
Qiu Sun ₁ , Constantin G Daniliuc ₁ , Christian Mück-Lichtenfeld ₁ , Klaus Bergander ₁ , Gerald Kehr ₁ , Gerhard Erker ₁

Affiliation

An intramolecular ethylene-bridged PH/BH system, isolated as a dimer, reduces carbon monoxide to the -CH2-O- state. In the presence of B(C6F5)3 the frustrated PH/BH Lewis pair reacts with carbon monoxide to give the product of reductive coupling of two CO molecules at the template. Removal of the B(C6F5)3 borane with pyridine leads to liberation of one equiv. of carbon monoxide to give a cyclic five-membered P(=O)-CH2-B com-pound, the product of reductive cleavage of carbon monoxide. It reacts as a borylated Horner P(=O)CH2B carbon nucleophile with carbon dioxide to give a bicyclic product by P-CH2 attack on CO2 combined with internal P=O to boron coordination.

中文翻译：

反应性邻位受阻 PH/BH Lewis 对对 CO 分子的还原裂解。

以二聚体形式分离的分子内乙烯桥连 PH/BH 系统将一氧化碳还原为 -CH2-O- 状态。在 B(C6F5)3 存在下，受阻的 PH/BH 路易斯对与一氧化碳反应，生成两个 CO 分子在模板上还原偶联的产物。用吡啶去除 B(C6F5)3 硼烷导致释放一当量。一氧化碳生成环状五元 P(=O)-CH2-B 化合物，这是一氧化碳还原裂解的产物。它作为硼酸化的霍纳 P(=O)CH2B 碳亲核试剂与二氧化碳反应，通过 P-CH2 攻击 CO2 结合内部 P=O 与硼配位，得到双环产物。

更新日期：2020-09-16

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