Institut für Anorganische Chemie, Julius-Maximilians-Universität Würzburg, Am Hubland, 97074 Würzburg, Germany.
J Am Chem Soc. 2013 Feb 13;135(6):2313-20. doi: 10.1021/ja310895w. Epub 2013 Jan 31.
In early reports, the boron atom of the anionic borido complexes {(η(5)-C(5)H(4)R)(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(PCy(3))(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.
在早期的报道中，阴离子硼化物配合物{(η(5)-C(5)H(4)R)(OC)(2)Mn}(2)B（R = H，Me）中的硼原子在亲电试剂如甲基碘和第 11 族金属氯化物的存在下表现出亲核行为，类似于山下和野崎开创性的硼化锂。后来，与著名的过渡金属路易斯碱[Pt(PCy(3))(2)]的反应表明硼中心可能具有亲电性。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 族金属较重卤化物的亲核取代。同时，发现其他第 11 族卤化物与硼中心相互作用，但形成的结构与金不同。通过计算探讨了阴离子对主族和过渡金属卤化物的选择性的基础，并讨论了阴离子的双功能、两性反应性。
