Xu Yu-He, Tkachenko Nikolay V, Popov Ivan A, Qiao Lei, Muñoz-Castro Alvaro, Boldyrev Alexander I, Sun Zhong-Ming
State Key Laboratory of Elemento-Organic Chemistry, Tianjin Key Lab for Rare Earth Materials and Applications, School of Materials Science and Engineering, Nankai University, Tianjin, China.
Department of Chemistry and Biochemistry, Utah State University, Logan, UT, USA.
Nat Commun. 2021 Jul 22;12(1):4465. doi: 10.1038/s41467-021-24706-4.
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(CO)SnSb] (M = Cr, Mo), and [(MSnSb)], (M = Cu, Ag)) in the process of capturing the hypho- [SnSb] 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 σ-aromatic units, producing a spherical aromatic shielding region in the cages. While in the case of [Mo(CO)SnSb] stabilization arises from locally σ-aromatic three-centre and five-centre two-electron bonds, aromatic islands in [(AgSnSb)] and [(CuSnSb)] render them globally antiaromatic. This work describes the coordination chemistry of the versatile building block [SnSb], thus providing conceptual advances in the field of metal-metal bonding in clusters.
异金属簇合物因其多样的配位模式以及在多相催化中的潜在应用，在合成化学领域引起了广泛关注。在此，我们报告了在乙二胺（en）溶液中捕获hypo-[SnSb]过程中，四种三元簇合物（[M(CO)SnSb] （M = Cr, Mo），以及[(MSnSb)]，（M = Cu, Ag））的合成、实验和理论表征。我们表明，二元阴离子与过渡金属离子或片段的配位由于局部σ-芳香单元的形成而提供了额外的稳定性，在笼中产生了一个球形芳香屏蔽区域。而在[Mo(CO)SnSb]的情况下，稳定性源于局部σ-芳香三中心和五中心双电子键，[(AgSnSb)]和[(CuSnSb)]中的芳香岛使其整体呈反芳香性。这项工作描述了多功能结构单元[SnSb]的配位化学，从而为簇合物中金属-金属键合领域提供了概念上的进展。
