Towards Homoleptic Borylene Complexes: Incorporation of Two Borylene Ligands into a Mononuclear Iridium Species
Towards Homoleptic Borylene Complexes: Incorporation of Two Borylene Ligands into a Mononuclear Iridium Species
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DOI：
10.1002/anie.201004103
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发表时间：
2010-01-01
影响因子：
16.6
通讯作者：
Radacki, Krzysztof
中科院分区：
文献类型：
--
作者：
Bertsch, Stefanie;Braunschweig, Holger;Radacki, Krzysztof
将低价第13族配体引入过渡金属的配位层中一直是一项具有挑战性的任务，特别是在形成均配配合物时。虽然在过去几十年中亚稳态或空间保护的低价EI（E= Al，Ga，In）前体已经变得可获得，[1]例如，EI卤化物，[1，2][{Cp* E} n]（Cp*= η5-C5 Me 5），[1，3]和[{EC（SiMe 3）3} n]，[1，4]稳定且可分离的硼同系物仍然没有被制备。为此，迄今为止仅实现了具有Al-、Ga-和In-基配体的均配过渡金属络合物，例如单核[Ni（ECp*）4]（A; E= Al，Ga）[5，6]和[Ni {EC（SiMe 3）3} 4]（B; E= Ga，In）[7，8]以及具有两个或更多个EI配体的许多混配实例。[9]相应的低价硼配体，即硼烯，仅在过渡金属的配位层中直接产生[10]，形成诸如[（OC）5 M = BN（SiMe 3）2]（C; M= Cr，Mo，W）的物质。[11]迄今为止，含有多于一个亚硼基取代基的单核亚硼基络合物以及均配亚硼基物种都持续抵抗分离。尽管如此，亚硼基络合物已经在基础有机金属研究中引起了越来越多的兴趣，因为它们与重要的有机金属化合物如卡宾、碳炔和亚乙烯基络合物的密切关系，以及亚硼基络合物的相似性。
The incorporation of subvalent Group 13 ligands into the coordination sphere of transition metals has always been a challenging task, particularly in the formation of homoleptic complexes. Although metastable or sterically protected subvalent EI (E= Al, Ga, In) precursors have become accessible during the last few decades,[1] for example, EI halides,[1, 2][{Cp* E} n](Cp*= η5-C5Me5),[1, 3] and [{EC (SiMe3) 3} n],[1, 4] stable and isolable boron congeners have still not been prepared. For this reason, only homoleptic transition-metal complexes with Al-, Ga-, and In-based ligands have so far been realized, for example, mononuclear [Ni (ECp*) 4](A; E= Al, Ga)[5, 6] and [Ni {EC (SiMe3) 3} 4](B; E= Ga, In),[7, 8] as well as numerous heteroleptic examples with two or more EI ligands.[9]The corresponding subvalent boron ligands, that is, borylenes, have only been generated directly in the coordination sphere of transition metals [10] to form species such as [(OC) 5M= BN (SiMe3) 2](C; M= Cr, Mo, W).[11] To date, both mononuclear borylene complexes containing more than one borylene substituent as well as homoleptic borylene species have continuously resisted isolation. Nonetheless, borylene complexes have sparked increasing interest in fundamental organometallic research because of their close relationship with important organometallic compounds such as carbene, carbyne, and vinylidene complexes, and the similarity of the