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 ([M2(CO)6Sn2Sb5]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 σ-aromatic units, producing a spherical aromatic shielding region in the cages. While in the case of [Mo2(CO)6Sn2Sb5]3− stabilization arises from locally σ-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.
Highlights
Heterometallic clusters have attracted broad interests in the synthetic chemistry due to their various coordination modes and potential applications in heterogeneous catalysis
The first structural determination of a Zintl anion was made by Kummer and Diehl in the 1970s, when they revealed the presence of [Sn9]4− cluster, which was subsequently used as a precursor for the synthesis of many polystannides[1]
The ESI mass spectrum (Fig. 2b, Supplementary Figs. 10–25) combined with Energy dispersive X-ray (EDX) data (Supplementary Figs. 26–29) confirms a 2:5 Sn:Sb ratio in all four clusters, while X-ray diffraction confirmed the positions of the heavy atoms in the clusters
Summary
Heterometallic clusters have attracted broad interests in the synthetic chemistry due to their various coordination modes and potential applications in heterogeneous catalysis. We adopted self-assembly as a synthetic strategy to synthesize a series of large Au/Pb clusters [Au8Pb33]6−, [Au12Pb44]8−, constructed from a nido-type cluster [AuPb11]3− 25. As part of this ongoing study, we aim to build metal clusters using other unnoticed Zintl precursors and the solid-state Zintl phase “K8SnSb4” came into our sight[26]. We report the syntheses and characterizations of these clusters [M2(CO)6Sn2Sb5]3− (M = Cr, 1; Mo, 2), [(MSn2Sb5)2]4− (M = Ag, 3; Cu, 4) This series corresponds to a vertex supplement process, from hypho- to arachno-, and to nido- type. It is found that the solid phase “K8SnSb4” could act as a versatile precursor to construct multinary cluster anions, and [Sn2Sb5]3− may serve as a potential building unit for further reactions
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