H 2 evolution from H 2 O via O–H oxidative addition across a 9,10-diboraanthracene
H 2 evolution from H 2 O via O–H oxidative addition across a 9,10-diboraanthracene
复制标题
H 2 O 通过 9,10-二硼蒽氧化加成从 H 2 O 演化出 H 2
DOI：
10.1039/d0cc05261b
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发表时间：
2020
影响因子：
4.9
通讯作者：
Harman, W. Hill
中科院分区：
文献类型：
--
作者：
Taylor, Jordan W.;Harman, W. Hill
本文报道了硼金配合物[Au（B2 P2）][K（18-c-6）];（B2 P2，9，10-bis（2-（diisopropylphosphino）-phenyl）-9，10-dihydroboranthrene）及其相应的双电子氧化配合物Au（B2 P2）Cl的水反应性。Au（B2 P2）Cl对H2O有耐受性，在H2O和三乙胺存在下，形成氢氧化物配合物Au（B2 P2）OH。[Au（B2 P2）]Cl和[Au（B2 P2）]OH是通过Gutmann-Becket方法判断的贫刘易斯酸，其中[Au（B2 P2）]OH显示DBA环的B原子之间的容易的氢氧化物交换，如通过变温NMR光谱所证明的。还原的硼金络合物[Au（B2 P2）]−与1当量的H2O反应生成氢化物/氢氧化物产物[Au（B2 P2）（H）（OH）]−，在进一步的H2O反应中迅速放出H2，生成二氢氧化物化合物[Au（B2 P2）（OH）2]−。[Au（B2 P2）]Cl可以通过HCl·Et 2 O从[Au（B2 P2）（OH）2]−再生，提供了通过在二硼蒽单元处的O-H氧化加成实现的从H2O放出H2的合成循环。
The water reactivity of the boroauride complex ([Au(B2P2)][K(18-c-6)]; (B2P2, 9,10-bis(2-(diisopropylphosphino)-phenyl)-9,10-dihydroboranthrene) and its corresponding two-electron oxidized complex, Au(B2P2)Cl, are presented. Au(B2P2)Cl is tolerant to H2O and forms the hydroxide complex Au(B2P2)OH in the presence of H2O and triethylamine. [Au(B2P2)]Cl and [Au(B2P2)]OH are poor Lewis acids as judged by the Gutmann–Becket method, with [Au(B2P2)]OH displaying facile hydroxide exchange between B atoms of the DBA ring as evidenced by variable temperature NMR spectroscopy. The reduced boroauride complex [Au(B2P2)]− reacts with 1 equivalent of H2O to produce a hydride/hydroxide product, [Au(B2P2)(H)(OH)]−, that rapidly evolves H2 upon further H2O reaction to yield the dihydroxide compound, [Au(B2P2)(OH)2]−. [Au(B2P2)]Cl can be regenerated from [Au(B2P2)(OH)2]−via HCl·Et2O, providing a synthetic cycle for H2 evolution from H2O enabled by O–H oxidative addition at a diboraanthracene unit.