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一种分子硼金化物:阴离子金的给体-受体配合物。

A Molecular Boroauride: A Donor-Acceptor Complex of Anionic Gold.

机构信息

Department of Chemistry, University of California-Riverside, Riverside, CA, 92521, USA.

Organic Chemistry & Catalysis, Debye Institute for Nanomaterials Science, Utrecht University, Universiteitsweg 99, 3584 CG, Utrecht, The Netherlands.

出版信息

Angew Chem Int Ed Engl. 2017 Aug 21;56(35):10413-10417. doi: 10.1002/anie.201703235. Epub 2017 Jun 27.

Abstract

Gold is unique among the transition metals in that it is stable as an isolated anion (auride). Despite this fact, the coordination chemistry of anionic gold is virtually nonexistent, and this unique oxidation state is not readily exploited in conventional solution chemistry owing to its high reactivity. Through the use of a new molecular scaffold based on diboraanthracene (B P , 1), we have overcome these issues by avoiding the intermediacy of zerovalent gold and stabilizing the highly reduced gold anion through acceptor interactions. We have thus synthesized a molecular boroauride [(B P )Au] ([2] ) and showed its reversible conversion between Au and Au states. Through a combination of spectroscopic and computational studies, we show the neutral state to be a Au complex with a ligand radical anion. Bonding analyses (NBO and QTAIM) and the isolobal relationship between gold and hydrogen provide support for the description of [2] as a boroauride complex.

摘要

金在过渡金属中是独特的,因为它作为一个孤立的阴离子(金负离子)是稳定的。尽管如此,阴离子金的配位化学实际上是不存在的,而且由于其高反应性,这种独特的氧化态在传统的溶液化学中不易被利用。通过使用基于二硼蒽(B P ,1)的新型分子支架,我们通过避免零价金的中间体并通过受体相互作用稳定高度还原的金负离子来克服这些问题。我们已经合成了一个分子硼金负离子[(B P )Au]([2]),并证明了其在 Au 和 Au 态之间的可逆转换。通过光谱和计算研究的结合,我们表明中性态是一个具有配体自由基阴离子的 Au 配合物。键分析(NBO 和 QTAIM)和金与氢之间的等电子关系为将[2]描述为硼金负离子配合物提供了支持。

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