Recent Advances in Aromatic Antimony Clusters

Li, Leijiao; Ali, Basharat; Chen, Zhongfang; Sun, Zhong‐Ming

doi:10.1002/cjoc.201800251

Cited by 9 publications

(6 citation statements)

References 89 publications

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“…The AdNDP method can represent a chemical bonding pattern in terms of both Lewis bonding elements (lone pairs (1c–2e) and 2c–2e bonds) as well as delocalized bonding elements (such as nc–2e ( n > 2) bonds), while the latter are usually associated with the concepts of aromaticity and antiaromaticity. This technique has been widely used in describing chemical bonding pattern of various Zintl clusters 41 – 47 . The chemical bonding of [Sn 2 Sb 5 ] 3− can be entirely described in terms of the classical 1c–2e and 2c–2e bonds (Supplementary Fig.…”

Section: Resultsmentioning

confidence: 99%

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

Tkachenko

Popov

et al. 2021

Nat Commun

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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.

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Section: Resultsmentioning

confidence: 99%

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

Tkachenko

Popov

et al. 2021

Nat Commun

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“…Recently, attempts have been made to evaluate the bonding in intermetalloid clusters by applying the concepts of (anti)aromaticity in cases that show multicenter bonding. 101,102 However, well-established quantum chemical concepts, including the superatom concept 103,104 or the related jellium model, 97,105 which rely on cluster orbitals, can be used more generally and more quantitatively for all kinds of multicenter bonding in polyatomic molecules. Endohedral clusters are presented first, followed by coordination-type compounds and heterometallic clusters.…”

Section: Gebr Lihypmentioning

confidence: 99%

Intermetalloid and Heterometallic Clusters Combining p-Block (Semi)Metals with d- or f-Block Metals

et al. 2019

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Clusters have been the subject of intense investigations since their famous definition launched by Cotton in 1963, and the area has expanded ever since. One obvious development addresses the widening of the definition of what to call a cluster: from purely (transition) metal−metal linked assemblies, as per Cotton's early denomination, to nonmetal/metal clusters or purely nonmetal cages, like fullerenes, and even noncovalent aggregates such as water clusters. The other extension concerns the broadened spectrum of compositions within the aforementioned cluster types and their corresponding structures that range from trinuclear motifs to clusters with sizes in the range of the hemoglobin unit. This review article reports on one cluster family that has its origins in traditional Zintl anion chemistry but has undergone rapid development in recent years, namely, ligand-free clusters that combine main group and transition metal atoms. Depending on the position of the transition metal atom(s), one refers to such clusters as intermetalloid (endohedral) clusters or as a special type of heterometallic clusters. The predominant synthetic access makes use of soluble Zintl anions. Other pathways for their preparation include traditional solid state reactions of according element combinations or bottom-up syntheses employing low valent organo-main group element sources. This survey will shed light on all of these approaches, with an emphasis on the syntheses that employ soluble Zintl anion compounds. The article will give a comprehensive overview of the currently known compounds, their different synthesis protocols, and analytic techniques for determination of their compositions, structures, and further properties. Additionally, this survey will report peculiarities of bonding situations found within some of the cluster molecules, which were studied by means of sophisticated quantum chemical investigations.

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“…Polar intermetallic compounds, also known as Zintl phases, generally represent compounds composed of s-block elements and p-block (semi)metal elements and can be transferred into Zintl salts by extraction with a cation-sequestering agent. Anionic clusters that are prepared by reactions of a Zintl phase or a Zintl salt with d-block or f-block metal compounds in solution are consequently referred to as Zintl clusters. − …”

Section: Introductionmentioning

confidence: 99%

Effect of La³⁺ on the Formation of Endohedral Zintl Clusters Featuring In/Bi Shells

Pan,

Weinert,

Dehnen

2024

Inorg. Chem.

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Investigating the interactions of f-block metal ions with p-block polyanions in multinary cluster compounds is becoming increasingly attractive but remains a challenge in terms of both the synthetic approach and the control of the structures that are formed during the syntheses. So far, two types of reactions were dominant for the formation of corresponding clusters: the reaction of binary anions of p-block elements in 1,2-diamino-ethane (en) solutions or the reaction of organobismuth compounds with corresponding f-block metal complexes in THF. Herein, we report the synthesis of [La@In 2 Bi 11 ] 4− (1) and its doubly μ-Bi-bridged analogue in the doubly4 1 and [K(crypt-222)] 4 2, respectively, achieved by reactions of [InMes 3 ] and [La(C 5 Me 4 H) 3 ] (Mes = mesityl, C 5 Me 4 H = tetramethylcyclopentadienyl) with K 10 Ga 3 Bi 6.65 / crypt-222 (crypt-222 = 4,7,13,16,21,24-hexaoxa-1,10-diazabicyclo[8.8.8]hexacosane) in en. In the absence of [La(C 5 Me 4 H) 3 ], the otherwise unchanged reactions afford the anions [Bi 6 (InMes)(InMes 2 )] 3− (3) and [Mes 3 In−InMes 3 ] 2− (4) instead, which can be isolated as their [K(crypt-222)] + salts [K(crypt-222)] 3 3 and [K(crypt-222)] 2 4•tol (tol = toluene), respectively. The {Bi 6 } fragment observed in anion 3 is assumed to be one of the key intermediates not only toward the formation of 1 and 2 but also on the way to more general bismuth rich compounds.

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Recent Advances in Aromatic Antimony Clusters

Cited by 9 publications

References 89 publications

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

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

Intermetalloid and Heterometallic Clusters Combining p-Block (Semi)Metals with d- or f-Block Metals

Effect of La³⁺ on the Formation of Endohedral Zintl Clusters Featuring In/Bi Shells

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Recent Advances in Aromatic Antimony Clusters

Cited by 9 publications

References 89 publications

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

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

Intermetalloid and Heterometallic Clusters Combining p-Block (Semi)Metals with d- or f-Block Metals

Effect of La3+ on the Formation of Endohedral Zintl Clusters Featuring In/Bi Shells

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Effect of La³⁺ on the Formation of Endohedral Zintl Clusters Featuring In/Bi Shells