Ditopic Ambiphilicity of an Anionic Dimetalloborylene Complex
Ditopic Ambiphilicity of an Anionic Dimetalloborylene Complex
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DOI：
10.1021/ja310895w
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发表时间：
2013-02-13
影响因子：
15
通讯作者：
Vargas, Alfredo
中科院分区：
文献类型：
--
作者：
Braunschweig, Holger;Damme, Alexander;Vargas, Alfredo
在早期报道中，阴离子硼络合物[{(eta(5)-C5H4R)(OC)(2)Mn}(2)B](-) (R = H, Me)的硼原子在甲基碘和第11族金属氯化物等亲电子试剂存在下表现出亲核行为，类似于Yamashita和Nozaki的突破性硼基锂。后来，与众所周知的过渡金属路易斯碱[Pt(PCy3)(2)]的反应表明了以硼为中心的亲电性的可能性。在本文中，我们阐明了阴离子的第三种反应性特征，即锰中心对第 14 族金属的较重卤化物的亲核取代。与此同时，其他 11 族卤化物被发现与硼中心相互作用，但形成与金不同的结构。通过计算探讨了区分主族和过渡金属卤化物阴离子的基础，并讨论了阴离子的双位、两亲反应性。
In early reports, the boron atom of the anionic borido complexes [{(eta(5)-C5H4R)(OC)(2)Mn}(2)B](-) (R = H, Me) showed nucleophilic behavior in the presence of electrophiles such as methyl iodide and group 11 metal chlorides, akin to the ground-breaking boryl lithium of Yamashita and Nozaki. Later, a reaction with the well-known transition metal Lewis base [Pt(PCy3)(2)] suggested the possibility of boron-centered electrophilicity. In this paper we elucidate a third reactivity profile of the anion, nucleophilic substitution on heavier halides of group 14 metals by a manganese center. Meanwhile, other group 11 halides were found to interact with the boron center, but form structures different from those seen with gold. The basis of the discrimination of the anion between main group and transition metal halides is explored computationally, and the ditopic, ambiphilic reactivity of the anions is discussed.