Ternary aromatic and anti-aromatic clusters derived from the hypho species [Sn2Sb5]3−

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论文题目:Ternary aromatic and anti-aromatic clusters derived from the hypho species [Sn2Sb5]3−

论文作者:Yuhe Xu, Nikolay V. Tkachenko, Ivan A. Popov, Lei Qiao, Alvaro Muñoz-Castro, Alexander I.Boldyrev, Zhongming Sun*

发表期刊:Nature Communications, 12(1), 4465, 2021    

Abstract: 

Heterometallic clusters have attracted broad interests in the synthetic  chemistry due to their various coordination modes and potential  applications in heterogeneous catalysis. Here we report the synthesis,  experimental, and theoretical characterizations of four ternary clusters  ([M-2(CO)(6)Sn2Sb5](3-) (M = Cr, Mo), and [(MSn2Sb5)(2)](4-), (M = Cu,  Ag)) in the process of capturing the hypho- [Sn2Sb5](3-) in  ethylenediamine (en) solution. We show that the coordination of the  binary anion to transition-metal ions or fragments provides additional  stabilization due to the formation of locally a-aromatic units,  producing a spherical aromatic shielding region in the cages. While in  the case of [Mo-2(CO)(6)Sn2Sb5](3-) stabilization arises from locally  a-aromatic three-centre and five-centre two-electron bonds, aromatic  islands in [(AgSn2Sb5)(2)](4-) and [(CuSn2Sb5)(2)](4-) render them  globally antiaromatic. This work describes the coordination chemistry of  the versatile building block [Sn2Sb5](3-), thus providing conceptual  advances in the field of metal-metal bonding in clusters.