Bousrez Guillaume, Harakat Dominique, Chevreux Sylviane, Déchamps-Olivier Isabelle, Jaroschik Florian
Université de Reims Champagne Ardenne, CNRS UMR 7312, ICMR, URCATech, 51100 Reims, France.
Department of Biological and Chemical Engineering, Aarhus University, 8000 Aarhus C, Denmark.
Dalton Trans. 2024 Sep 24;53(37):15595-15601. doi: 10.1039/d4dt02004a.
The reduction of titanocene dichloride CpTiCl with lanthanide metals has led to the discovery of a surprising lanthanide effect: while with most lanthanides, a divalent [CpTi] equivalent was obtained, the use of samarium or ytterbium only led to the reduction to trivalent [CpTiCl]-type complexes, including the structurally characterized heterobimetallic complex [CpTi(μ-Cl)SmCl(THF)]. These results were corroborated by reactivity studies (alkyne coupling and radical reactions), EPR spectroscopy and electrospray mass spectrometry, providing new insights into the reduction chemistry of lanthanide metals.
用镧系金属还原二氯二茂钛（CpTiCl₂）导致了一个惊人的镧系效应的发现：虽然与大多数镧系金属反应可得到二价的[CpTi]等价物，但使用钐或镱时仅会还原为三价的[CpTiCl]型配合物，包括结构已表征的异双金属配合物[CpTi(μ-Cl)SmCl(THF)]。这些结果通过反应性研究（炔烃偶联和自由基反应）、电子顺磁共振光谱和电喷雾质谱得到了证实，为镧系金属的还原化学提供了新的见解。
