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手性金(I)/铑(I)双金属对协同引发配体非等药性和键活化。

Polarized Au(I)/Rh(I) bimetallic pairs cooperatively trigger ligand non-innocence and bond activation.

机构信息

Instituto de Investigaciones Químicas (IIQ), Departamento de Química Inorgánica and Centro de Innovación en Química Avanzada (ORFEO-CINQA), Consejo Superior de Investigaciones Científicas (CSIC) and University of Sevilla, Avenida Américo Vespucio 49, 41092 Sevilla, Spain.

出版信息

Dalton Trans. 2023 Mar 21;52(12):3835-3845. doi: 10.1039/d3dt00410d.

DOI:10.1039/d3dt00410d
PMID:36866716
原文链接:https://pmc.ncbi.nlm.nih.gov/articles/PMC10029337/
Abstract

The combination of molecular metallic fragments of contrasting Lewis character offers many possibilities for cooperative bond activation and for the disclosure of unusual reactivity. Here we provide a systematic investigation on the partnership of Lewis basic Rh(I) compounds of type [(η-L)Rh(PR)] (η-L = (CMe) or (CH)) with highly congested Lewis acidic Au(I) species. For the cyclopentadienyl Rh(I) compounds, we demonstrate the non-innocent role of the typically robust (CMe) ligand through migration of a hydride to the Rh site and provide evidence for the direct implication of the gold fragment in this unusual bimetallic ligand activation event. This process competes with the formation of dinuclear Lewis adducts defined by a dative Rh → Au bond, with selectivity being under kinetic control and tunable by modifying the stereoelectronic and chelating properties of the phosphine ligands bound to the two metals. We provide a thorough computational study on the unusual Cp* non-innocent behavior and the divergent bimetallic pathways observed. The cooperative FLP-type reactivity of all bimetallic pairs has been investigated and computationally examined for the case of N-H bond activation in ammonia.

摘要

分子金属片段的路易斯性质的组合提供了许多合作键活化的可能性，也为揭示不寻常的反应性提供了可能。在这里，我们对路易斯碱性 Rh(I)化合物[(η-L)Rh(PR)]（η-L = (CMe) 或 (CH))与高度拥挤的路易斯酸性 Au(I)物种的伙伴关系进行了系统的研究。对于环戊二烯基 Rh(I)化合物，我们通过氢化物向 Rh 位的迁移证明了通常稳定的(CMe)配体的非惰性作用，并提供了金片段直接参与这种不寻常的双金属配体活化事件的证据。这个过程与通过形成 dative Rh → Au 键定义的双核路易斯加合物竞争，选择性受动力学控制，并可通过修饰与两种金属结合的膦配体的立体电子和螯合性质进行调节。我们对观察到的不寻常的 Cp*非惰性行为和发散的双金属途径进行了全面的计算研究。我们还对所有双金属对的协同 FLP 型反应性进行了研究，并对氨中 N-H 键活化的情况进行了计算研究。

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