Multiple complexation of CO and related ligands to a main-group element
Multiple complexation of CO and related ligands to a main-group element
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DOI：
10.1038/nature14489
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发表时间：
2015-06-18
期刊：
影响因子：
64.8
通讯作者：
Ye, Qing
中科院分区：
文献类型：
--
作者：
Braunschweig, Holger;Dewhurst, Rian D.;Ye, Qing
原子或分子片段结合多个一氧化碳（CO）分子以形成多羰基加合物的能力是过渡金属的基本特性。过渡金属羰基配合物对工业至关重要，天然存在于许多酶（如氢化酶）的活性位点，是有前途的治疗剂（1），甚至在星际尘埃云中也被观察到（2）。尽管已经建立了丰富的过渡金属多羰基配合物（3），但还没有周期表第4至12族以外的元素直接与两个或更多个CO单元反应形成稳定的多羰基加合物。在这里，我们提出了一种硼烯二羰基配合物的合成，这是第一个使用CO制备的主族元素的多羰基配合物。该化合物还对环境空气和水分稳定。所使用的合成策略-使用供体配体从过渡金属中释放亚硼基配体-是广泛适用的，导致许多具有不同刘易斯碱性基团的前所未有的单价硼物种。这些化合物与传统的过渡金属羰基络合物的相似性通过CO的光解释放和随后的分子内碳-碳键活化来证明。
The ability of an atom or molecular fragment to bind multiple carbon monoxide (CO) molecules to form multicarbonyl adducts is a fundamental trait of transition metals. Transition-metal carbonyl complexes are vital to industry, appear naturally in the active sites of a number of enzymes (such as hydrogenases), are promising therapeutic agents(1), and have even been observed in interstellar dust clouds(2). Despite the wealth of established transition-metal multicarbonyl complexes(3), no elements outside groups 4 to 12 of the periodic table have yet been shown to react directly with two or more CO units to form stable multicarbonyl adducts. Here we present the synthesis of a borylene dicarbonyl complex, the first multicarbonyl complex of a main-group element prepared using CO. The compound is additionally stable towards ambient air and moisture. The synthetic strategy used-liberation of a borylene ligand from a transition metal using donor ligands-is broadly applicable, leading to a number of unprecedented monovalent boron species with different Lewis basic groups. The similarity of these compounds to conventional transition-metal carbonyl complexes is demonstrated by photolytic liberation of CO and subsequent intramolecular carbon-carbon bond activation.