Reversible addition of ethylene to a pincer-based boryl-iridium unit with the formation of a bridging ethylidene,Chemical Science

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Reversible addition of ethylene to a pincer-based boryl-iridium unit with the formation of a bridging ethylidene
Chemical Science ( IF 7.6 ) Pub Date : 2020-10-05 , DOI: 10.1039/d0sc04748a
Yihan Cao _{1,

2,

3} , Wei-Chun Shih _{1,

2,

3} , Nattamai Bhuvanesh _{1,

2,

3} , Oleg V. Ozerov _{1,

2,

3}

Affiliation

This report examines reactions of a series of Ir complexes supported by the diarylboryl/bis(phosphine) PBP pincer ligand with ethylene: (PBP)IrH₄ (1), (PBP)IrH₂(CO) (2), and (PBP)Ir(CO)₂ (3). The outcomes of these reactions differ from those typical for Ir complexes supported by other pincer ligands and do not give rise to simple ethylene adducts or products of insertion of Ir into the C–H bond of ethylene. Instead, the elements of ethylene are incorporated into the molecules to result in B–C bonds. In the case of 2 and 3, ethylene addition results in the formation of B/Ir bridging ethylidene complexes 5 and 6. For 6, the addition of ethylene (and the analogous addition of 1-hexene) is shown to be partially reversible. Addition of ethylene to 2 and 3 is remarkable because they are saturated at Ir and yet the net outcome is such that ethylene binds without replacing any ligands already present. A mechanistic inquiry suggests that dissociation of CO from 3 or 6 is necessary in order for the addition or loss of ethylene to proceed.

中文翻译：

将乙烯可逆地添加到基于钳的硼-铱单元中，形成桥联亚乙基

该报告研究了由二芳基硼基/双（膦）PBP钳位配体支持的一系列Ir配合物与乙烯的反应：（PBP）IrH ₄（1），（PBP）IrH ₂（CO）（2）和（PBP） Ir（CO）₂（3）。这些反应的结果不同于其他夹钳配体所支持的Ir络合物的典型反应结果，并且不会产生简单的乙烯加合物或Ir插入乙烯C–H键的产物。取而代之的是，将乙烯元素掺入分子中以形成B–C键。在2和3的情况下，乙烯的添加导致B / Ir桥联亚乙基络合物5的形成。和6。对于6，显示乙烯的添加（和1-己烯的类似添加）是部分可逆的。乙烯加到2和3上是很重要的，因为它们在Ir处饱和，但是最终结果是乙烯结合而没有取代任何已经存在的配体。机理研究表明，为了使乙烯的添加或损失进行，必须将CO从3或6解离。

更新日期：2020-10-12

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