• Structures

Inner Template-Directed Synthesis of MOCs

 

Introduction. Multinuclear organometallic clusters (MOCs) and nanoclusters (MONCs) have been proposed as important but elusive intermediates in many metal catalytic processes. The steric hindrance effect of several metal species around a carbon center and the stabilization effect of multi-center bonding in MOCs reduce their reactivity and consequently allow us to achieve the ready isolation of polymetallic species. Based on the transformation of multi-functionalized organic substrates, various in situ generated polycarbanions act as inner templatesto adjust the nuclearity number and geometry of MOCs with high structural diversity.

 

Results. According to the Baldwin’s Rule, a great number of MOCs including [C2-M4] and [C-M4] species have been accomplished by the saturated coordination of organic reaction intermediates. For example, we employed a trinuclear gold(I) imido moiety to undergo an intramolecular attack on gold(I)-activated ethynyl to generate a tetra-aurated indole with a new type of hyperconjugative aromaticity. Thus, the concept of hyperconjugative aromaticity is firstly extended to aromatics containing transition metal substituents. Furthermore, we discovered an extended hyperconjugative aromaticity in a penta-aurated indolium that owns two vicinal gem-diaurated carbon atoms on an aromatic ring. This extended hyperconjugative aromaticity causes a better electron conjugation in the indolyl five-membered ring, thus enabling a facile protodeauration reaction. In addition, based on the cyclization reactions of enynes, we achieved a carbon dianion-centered Au11 cluster, which surprisingly exhibited high catalytic activity.

Yuan, J.; Sun, T.; He, X.; An, K.; Zhu, J.; Zhao, L. Nat. Commun.2016, 7, 11489; Xiao, K.; Zhao, Y.; Zhu, J.; Zhao, L. Nat. Commun.2019, 10, 5639.

 



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