Main Group Metal–Actinide Magnetic Coupling and Structural Response Upon U<sup>4+</sup> Inclusion Into Bi, Tl/Bi, or Pb/Bi Cages

Lichtenberger, Niels; Wilson, Robert J.; Eulenstein, Armin Rainer; Massa, Werner; Clérac, Rodolphe; Weigend, Florian; Dehnen, Stefanie

doi:10.1021/jacs.6b04363

Cited by 86 publications

(111 citation statements)

References 51 publications

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“…Reactions of transition‐metal, lanthanide, or even actinide organometallic reagents with homoatomic polyanions of Group 14, Group 15, and heteroatomic tetrahedral Group 14/15 or Group 13/15 anions provide a powerful route toward the synthesis of a variety of metal‐doped clusters. Selected examples represent ligand‐free monometallic doped clusters, such as [Ni@E 9 ] q − (E=Ge or Sn),, [Cu@E 9 ] 3− (E=Sn or Pb), [Ni@Pb 10 ] 2− , [M@Pb 12 ] x − (M=Ni, Pd, Pt, Mn, or Rh), [Ir@Sn 12 ] 3− , [U@Bi 12 ] 3− , and [Eu@Sn 6 Bi 8 ] 4− . So far, only a limited number of clusters with higher nuclearities ( n >14) involving more than one interstitial metal atom have been structurally characterized .…”

Section: Introductionmentioning

confidence: 99%

[Co₂@Ge₁₆]⁴⁻: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

Liu

Popov

et al. 2017

Chemistry A European J

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We report the successful isolation and structural elucidation of two bimetallic doped [Co @Ge ] clusters (α and β form), which were synthesized through the reaction of [{(ArN) CtBu}Co(η -toluene)] (Ar=2,6-diisopropylphenyl) and K Ge in ethylenediamine (en) solution and co-crystallized together in [K(2,2,2-crypt)] [Co @Ge ]⋅en. The α-[Co @Ge ] isomer prefers a distinct D 3-connected architecture, whereas the deltahedral isomeric β-[Co @Ge ] isomer adopts a quasi-C geometry and can be seen as coupling of two distorted arachno-[Co@Ge ] units. Chemical bonding analyses indicate that the skeleton of the α isomer is mainly composed of localized bonds, whereas only multicenter bonding interactions govern the geometry of the β isomer, which was further found to exhibit a fluxional behavior. The coexistence of both isomers within one unit cell links the 3-connected clusters with their deltahedral congeners, thus highlighting the structural and electronic flexibility of such discreet cluster systems.

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Section: Introductionmentioning

confidence: 99%

[Co₂@Ge₁₆]⁴⁻: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

Liu

Popov

et al. 2017

Chemistry A European J

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“…In en, [U(C 5 Me 4 H) 3 ] releases its (C 5 Me 4 H) − ligands in the presence of Bi 4 2− (formed in situ from (GaBi 3 ) 2− ) . Here, the ligands are replaced by three Bi 4 2− rings, resulting in a paramagnetic [U@Bi 12 ] 3− cluster.…”

Section: Formation Of Ligand‐free Metal Clustersmentioning

confidence: 99%

“… Calculated formation of [U@Bi 12 ] 3− by subsequent replacement of (C 5 Me 4 H) − ligands of the [U(C 5 Me 4 H) 3 ] precursor by in situ‐formed Bi 4 2− anions, which thereupon undergo Bi−Bi bond formation …”

Section: Formation Of Ligand‐free Metal Clustersmentioning

confidence: 99%

(Multi‐)Metallic Cluster Growth

Weinert

Mitzinger

Dehnen

2018

Chemistry A European J

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This review article provides a survey of contemporary investigations on main group metal cluster formation, addressing homo- and heterometallic clusters (including small numbers of transition metal atoms), with or without an external ligand shell, thereby excluding clusters with non-metal atoms as bridging ligands. Most of the studies reflected herein represent insights into the formation of intermediates from the starting material, or the final cluster formation from established intermediates. In rare cases, the entire process was suggested as a result of comprehensive, multi-method elucidations. The article is to be understood as a state-of-the-art report, as the subject matter is currently a rising field of research, which is still in its infancy, despite some early activities that date back to the 1980s. At the same time, the article intends to point toward both the importance and the feasibility of according studies, in order to encourage researchers to gain even more knowledge in this field. Only deep understanding of cluster formation will allow for design, and ultimately control, of their syntheses, with the long-term goal of their optimization and purposeful application in catalysis or novel material synthesis.

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“…Today,t hese terms are well used for av ariety of molecules, including inorganic compounds.A longside,t hese concepts have also gained huge popularity as more and more chemical species are being discovered, where delocalized bonding is used to describe the structures.I n1 995, Robinson and coworkers reported [3] thes ynthesis of Na 2 [[(2,4,6-Me 3 C 6 H 2 ) 2 C 6 H 3 ]Ga] 3 with two p electrons delocalized over the three gallium atoms that make the system p-aromatic according to the Hückel rule.Recently,the first solid-state allmetal p-antiaromatic compounds [Ln(h 4 -Sb 4 ) 3 ] 3À (Ln = La, Y, Ho,E r, Lu) were synthesized and characterized. [5] Thea romaticity/ antiaromaticity concept was also extended to bare metal clusters found in the gas phase. [5] Thea romaticity/ antiaromaticity concept was also extended to bare metal clusters found in the gas phase.…”

mentioning

confidence: 99%

“…[4] The [U@Bi 12 ] 3À anion with similar geometry was reported very recently by Dehnen and co-workers. [5] Thea romaticity/ antiaromaticity concept was also extended to bare metal clusters found in the gas phase. [6] Fort he first time,t he saromaticity concept was shown to be applicable to small alkali metal and alkaline earth metal clusters.…”

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confidence: 99%

Peculiar All‐Metal σ‐Aromaticity of the [Au₂Sb₁₆]⁴⁻ Anion in the Solid State

et al. 2016

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Gas-phase clusters are deemed to be s-aromatic when they satisfy the 4n + 2rule of aromaticity for delocalized s electrons and fulfill other requirements knownf or aromatic systems.W hile the range of nvalues was shown to be quite broad when applied to short-lived clusters found in molecularbeam experiments,s tability of all-metal cluster-like fragments isolated in condensed phase was previously shown to be mainly ascribed to two electrons (n = 0). In this work, the applicability of this concept is extended towards solid-state compounds by demonstrating au nique example of as torable compound, which was isolated as astable [K([2.2.2]crypt)] + salt, featuring a[ Au 2 Sb 16 ] 4À cluster core possessing two all-metal aromatic AuSb 4 fragments with six delocalized s electrons each (n = 1). This discovery pushes the boundaries of the original idea of KekulØ and firmly establishes the usefulness of the s-aromaticity concept as ag eneral idea for both small clusters and solid-state compounds.Although the original concept of aromaticity in chemistry was put forward by August KekulØ [1] more than 150 years ago, it currently occupies am assive niche in modern chemistry. [2] Theconcepts of p aromaticity/antiaromaticity were primarily used to explain chemical bonding in organic compounds. Today,t hese terms are well used for av ariety of molecules, including inorganic compounds.A longside,t hese concepts have also gained huge popularity as more and more chemical species are being discovered, where delocalized bonding is used to describe the structures.I n1 995, Robinson and coworkers reported [3] thes ynthesis of Na 2 [[(2,4,6-Me 3 C 6 H 2 ) 2 C 6 H 3 ]Ga] 3 with two p electrons delocalized over the three gallium atoms that make the system p-aromatic according to the Hückel rule.Recently,the first solid-state allmetal p-antiaromatic compounds [Ln(h 4 -Sb 4 ) 3 ] 3À (Ln = La, Y, Ho,E r, Lu) were synthesized and characterized. [4] The [U@Bi 12 ] 3À anion with similar geometry was reported very recently by Dehnen and co-workers. [5] Thea romaticity/ antiaromaticity concept was also extended to bare metal clusters found in the gas phase. [6] Fort he first time,t he saromaticity concept was shown to be applicable to small alkali metal and alkaline earth metal clusters. [7] Modern developments on aromaticity in various aromatic/antiaromatic chemical species composed of main-group elements and transition metals have been extensively reviewed elsewhere. [8][9][10][11] Fora ll all-metal aromatic fragments that have been synthesized in the solid state up to date,t here were only two delocalized electrons responsible for the s-aromaticity of the compounds,asexemplified by the cases of Pd 3 + ,Au 3 + ,and TiSn 2 clusters. [12][13][14] Thus far,w ea re not aware of any solidstate compounds containing two all-metal s-aromatic fragments involving six delocalized electrons each. Hence,the 6s-electron aromatic fragments found in the [Au 2 Sb 16 ] 4À cluster in this study expand the family of storable aromatic metal clusters thus solidifying ...

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Main Group Metal–Actinide Magnetic Coupling and Structural Response Upon U⁴⁺ Inclusion Into Bi, Tl/Bi, or Pb/Bi Cages

Cited by 86 publications

References 51 publications

[Co₂@Ge₁₆]⁴⁻: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

[Co₂@Ge₁₆]⁴⁻: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

(Multi‐)Metallic Cluster Growth

Peculiar All‐Metal σ‐Aromaticity of the [Au₂Sb₁₆]⁴⁻ Anion in the Solid State

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Main Group Metal–Actinide Magnetic Coupling and Structural Response Upon U4+ Inclusion Into Bi, Tl/Bi, or Pb/Bi Cages

Cited by 86 publications

References 51 publications

[Co2@Ge16]4−: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

[Co2@Ge16]4−: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

(Multi‐)Metallic Cluster Growth

Peculiar All‐Metal σ‐Aromaticity of the [Au2Sb16]4− Anion in the Solid State

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Main Group Metal–Actinide Magnetic Coupling and Structural Response Upon U⁴⁺ Inclusion Into Bi, Tl/Bi, or Pb/Bi Cages

[Co₂@Ge₁₆]⁴⁻: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

[Co₂@Ge₁₆]⁴⁻: Localized versus Delocalized Bonding in Two Isomeric Intermetalloid Clusters

Peculiar All‐Metal σ‐Aromaticity of the [Au₂Sb₁₆]⁴⁻ Anion in the Solid State