[Rh2(MEPY)4] and [BiRh(MEPY)4]: Convenient Syntheses and Computational Analysis of Strikingly Dissimilar Siblings,Helvetica Chimica Acta

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[Rh2(MEPY)4] and [BiRh(MEPY)4]: Convenient Syntheses and Computational Analysis of Strikingly Dissimilar Siblings
Helvetica Chimica Acta ( IF 1.5 ) Pub Date : 2021-04-21 , DOI: 10.1002/hlca.202100042
Lorenz E. Löffler ₁ , Michael Buchsteiner ₁ , Lee R. Collins ₁ , Fabio P. Caló ₁ , Santanu Singha ₁ , Alois Fürstner ₁

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[Rh₂(MEPY)₄] is a versatile catalyst for asymmetric synthesis but its preparation requires purification by chromatography on surface-modified silica. A higher yielding procedure based on a more convenient work-up is presented herein. Moreover, a much improved method for the preparation of [BiRh(OTfa)₄] is described, which makes this heterobimetallic complex readily available. Subsequent exchange of the trifluoroacetate ligands opens access to a so far underappreciated family of (chiral) paddlewheel complexes. While [BiRh] complexes comprising four carboxylate ligands are highly adequate for intermolecular asymmetric cyclopropanation reactions, [BiRh(MEPY)₄] as the heterobimetallic cousin of [Rh₂(MEPY)₄] was found to be surprisingly unreactive; DFT calculations uncover the reasons for this inertia.

中文翻译：

[Rh2(MEPY)4] 和 [BiRh(MEPY)4]：显着不同兄弟姐妹的便捷合成和计算分析

[Rh ₂ (MEPY) ₄ ] 是一种用于不对称合成的通用催化剂，但其制备需要通过表面改性二氧化硅色谱纯化。本文提出了基于更方便的后处理的更高产率的程序。此外，还描述了一种大大改进的 [BiRh(OTfa) ₄ ]制备方法，这使得这种异质双金属配合物易于获得。随后三氟乙酸酯配体的交换打开了获得迄今为止未被充分认识的（手性）桨轮复合物家族的途径。虽然包含四个羧酸盐配体的 [BiRh] 配合物非常适合分子间不对称环丙烷化反应，但 [BiRh(MEPY) ₄ ] 作为 [Rh ₂ (MEPY)的异双金属表亲₄ ] 出人意料地反应迟钝；DFT 计算揭示了这种惯性的原因。

更新日期：2021-06-15

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