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

A Molecular Boroauride: A Donor-Acceptor Complex of Anionic Gold.
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分子硼金:阴离子金的供体-受体复合物。

DOI:
10.1002/anie.201703235
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发表时间:
2017
期刊:
影响因子:
--
通讯作者:
W. Harman
W. Harman
中科院分区:
--
文献类型:
--
作者:
Jordan W. Taylor;Alex McSkimming;M. Moret;W. Harman

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金在过渡金属中是独特的,因为它作为孤立的阴离子(金化物)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,并且由于其高反应性,这种独特的氧化态在常规溶液化学中不容易被利用。通过使用基于二硼蒽(B2 P2,1)的新分子支架,我们通过避免零价金的中间性和通过受体相互作用稳定高度还原的金阴离子来克服这些问题。我们合成了一种分子硼金化合物[(B2 P2)Au]-([2]-),并证明了它在Au-I和AuI态之间的可逆转换。通过结合光谱和计算的研究,我们表明中性状态是一个AuI配合物与配体自由基阴离子。成键分析(NBO和QTAIM)和金与氢之间的等瓣关系为将[2]-描述为硼金络合物提供了支持。
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 (B2 P2 , 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 [(B2 P2 )Au]- ([2]- ) and showed its reversible conversion between Au-I and AuI states. Through a combination of spectroscopic and computational studies, we show the neutral state to be a AuI 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.
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影响因子: 16.6
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