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

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.

[Nb@Ge13/14]3−: New Family Members of Ge‐Based Intermetalloid Clusters

“…Previously, AdNDP has been shown to be a very efficient and visual approach for the interpretation of the molecular orbital-based wave functions for various systems with complex bonding patterns. [41][42][43] AdNDP was reported to be qualitatively insensitive to the level of theory used. [41,43,44] Specifically, it was found that as long as the basis set is large enough to sufficiently describe electronic structure, AdNDP showed no qualitative dependency on the basis set.…”

Between Elemental Match and Mismatch: From K12Ge3.5Sb6 to Salts of (Ge2Sb2)2−, (Ge4Sb12)4−, and (Ge4Sb14)4−

“…Upon addition of ZnPh 2 to such extractions, a complex of a corresponding 2 : 5 anion was obtained, [(ZnPh) 2 (Sn 2 Sb 5 )] 3− [8] . A partially oxidized version of this binary anion, “(Sn 2 Sb 5 ) 3− ”, was captured recently in transition metal complexes like [{Mo(CO) 3 } 2 (Sn 2 Sb 5 )] 3− [35] …”

“…[8] A partially oxidized version of this binary anion, "(Sn 2 Sb 5 ) 3À ", was captured recently in transition metal complexes like [{Mo-(CO) 3 } 2 (Sn 2 Sb 5 )] 3À . [35]…”

Missing Link in the Growth of Lead-Based Zintl Clusters: Isolation of the Dimeric Plumbaspherene [Cu4Pb22]4–

“…Our understanding of the mechanism of growth of these clusters from smaller component parts remains limited, although a small number of recent studies have begun to address this critical issue using a combination of X-ray crystallography, mass spectrometry, and computational analysis. 17,18 In the formation of the group-5 metal clusters [TaGe 8 As 4 ] 3− and [TaGe 8 As 6 ] 3− , for example, fusion of the known tetrahedral [Ge 2 As 2 ] 2− unit with the (unknown) Ta-containing fragments [TaGe 3 ] − and [Ta-Ge 4 As 2 ] − has been shown to provide a viable route to the isolated products. 17 The growth of even larger clusters containing multiple deltahedral units and/or transition metals, which offers the potential for a much wider range of M/E ratios along with the possibility of metal−metal bonding, presents a substantial synthetic challenge simply because the individual building blocks such as the ones shown in Figure 1 typically carry high negative charges.…”

“…The crystalline products are often highly sensitive to both air and moisture, but nevertheless a now extensive family of clusters with stoichiometries MPb 9–12 has been synthesized in this way, including [CuPb 9 ] 3– , [NiPb 10 ] 2– , [AgPb 11 ] 3– , [MPb 12 ] n − (M = Au, Ni, Pd, Pt, Co, Rh, Ir, Mn), and [(Cp*Ru)­CuPb 11 ] 2– (Figure ). Our understanding of the mechanism of growth of these clusters from smaller component parts remains limited, although a small number of recent studies have begun to address this critical issue using a combination of X-ray crystallography, mass spectrometry, and computational analysis. , In the formation of the group-5 metal clusters [TaGe 8 As 4 ] 3– and [TaGe 8 As 6 ] 3– , for example, fusion of the known tetrahedral [Ge 2 As 2 ] 2– unit with the (unknown) Ta-containing fragments [TaGe 3 ] − and [TaGe 4 As 2 ] − has been shown to provide a viable route to the isolated products …”