Revisiting the Bonding Model for Gold(I) Species: The Importance of Pauli Repulsion Revealed in a Gold(I)-Cyclobutadiene Complex.
Revisiting the Bonding Model for Gold(I) Species: The Importance of Pauli Repulsion Revealed in a Gold(I)-Cyclobutadiene Complex.
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DOI：
10.1002/anie.202202019
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发表时间：
2022-05-23
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了解金(I)的键合是金(I)催化发展的核心。本文介绍了首个金(I)-环丁二烯配合物的合成和表征，并用最先进的能量分解分析方法进行了键合分析。对新物种可能的配位模式的分析不仅证实了金(I)键的既定特征，而且表明泡利斥力是一个迄今为止被忽视的关键因素。此外，通过将金(I)-环丁二烯与p-、d-和f-嵌段金属稳定的同族化合物进行比较，我们获得了金(I)-键合的新视角。因此，我们改进了金(I)键模型，将泡利斥力和电荷转移的微妙相互作用作为各种配位基序的关键驱动力。泡利斥力同样被确定为Au(I)-炔类的重要相互作用，证实了对Au(I)键的修正理解。我们提出了一种新的Au(I)-环丁二烯配合物，其减少的泡利排斥产生一个η - 1而不是η - 4配位。这项实验和理论结合的研究激发了Au(I)-π-配体键模型的重新表述，将泡利排斥作为一个关键因素。对Au(I)-炔的进一步分析证实了这一结论。
Understanding the bonding of gold(I) species has been central to the development of gold(I) catalysis. Herein, we present the synthesis and characterization of the first gold(I)-cyclobutadiene complex, accompanied with bonding analysis by state-of-the-art energy decomposition analysis methods. Analysis of possible coordination modes for the new species not only confirms established characteristics of gold(I) bonding, but also suggests that Pauli repulsion is a key yet hitherto overlooked element. Additionally, we obtain a new perspective on gold(I)-bonding by comparison of the gold(I)-cyclobutadiene to congeners stabilized by p-, d-, and f-block metals. Consequently, we refine the gold(I) bonding model, with a delicate interplay of Pauli repulsion and charge transfer as the key driving force for various coordination motifs. Pauli repulsion is similarly determined as a significant interaction in Au(I)-alkyne species, corroborating this revised understanding of Au(I) bonding. We present a novel Au(I)-cyclobutadiene complex for which reduced Pauli repulsion yields an η1 instead of η4-coordination. This combined experimental and theoretical study motivates a reformulation of the Au(I)-π-ligand bonding model to include Pauli repulsion as a key element. Further analysis of Au(I)-alkynes corroborates this conclusion.
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