Taylor Jordan W, Harman W Hill
Department of Chemistry, University of California, Riverside, Riverside, CA 92521, USA.
Chem Commun (Camb). 2020 Nov 18;56(89):13804-13807. doi: 10.1039/d0cc05261b. Epub 2020 Oct 20.
The water reactivity of the boroauride complex ([Au(BP)][K(18-c-6)]; (BP, 9,10-bis(2-(diisopropylphosphino)-phenyl)-9,10-dihydroboranthrene) and its corresponding two-electron oxidized complex, Au(BP)Cl, are presented. Au(BP)Cl is tolerant to HO and forms the hydroxide complex Au(BP)OH in the presence of HO and triethylamine. [Au(BP)]Cl and [Au(BP)]OH are poor Lewis acids as judged by the Gutmann-Becket method, with [Au(BP)]OH displaying facile hydroxide exchange between B atoms of the DBA ring as evidenced by variable temperature NMR spectroscopy. The reduced boroauride complex [Au(BP)] reacts with 1 equivalent of HO to produce a hydride/hydroxide product, [Au(BP)(H)(OH)], that rapidly evolves H upon further HO reaction to yield the dihydroxide compound, [Au(BP)(OH)]. [Au(BP)]Cl can be regenerated from [Au(BP)(OH)]via HCl·EtO, providing a synthetic cycle for H evolution from HO enabled by O-H oxidative addition at a diboraanthracene unit.
本文介绍了硼金配合物（[Au(BP)][K(18-c-6)]；BP为9,10-双(2-(二异丙基膦基)-苯基)-9,10-二氢硼蒽）及其相应的双电子氧化配合物Au(BP)Cl的水反应活性。Au(BP)Cl对HO具有耐受性，在HO和三乙胺存在下形成氢氧化物配合物Au(BP)OH。根据古特曼-贝克特方法判断，[Au(BP)]Cl和[Au(BP)]OH是较弱的路易斯酸，变温核磁共振光谱表明[Au(BP)]OH在DBA环的B原子之间表现出容易的氢氧化物交换。还原的硼金配合物[Au(BP)]与1当量的HO反应生成氢化物/氢氧化物产物[Au(BP)(H)(OH)]，该产物在进一步与HO反应时迅速释放出H，生成二氢氧化物化合物[Au(BP)(OH)₂]。[Au(BP)]Cl可以通过HCl·EtO从[Au(BP)(OH)₂]再生，提供了一个由二硼蒽单元上的O-H氧化加成实现从HO释放H的合成循环。
