A Stannyl-Decorated Zintl Ion [Ge18Pd3(SniPr3)6]2–: Twinned Icosahedron with a Common Pd3-Face or 18-Vertex Hypho-Deltahedron with a Pd3-Triangle Inside

The reaction of [(Ge {Si(TMS) } PtBu )] with NHC CuCl yields [(Ge {Si(TMS) } )(tBu P)]Cu(NHC ) (1), which is a new derivative of the recently reported monomeric zwitterionic tetrel cluster compounds [(Ge {Si(TMS) } )(tBu P)]M(NHC ) (M: Cu, Ag, Au). By contrast, the reaction of the same anion [(Ge {Si(TMS) } PtBu )] with the more labile copper phosphine complex Cy PCuCl leads to the formation of [Ge {Si(TMS) } {(tBu) PCu} Ge {Si(TMS) } ] (2), which is a neutral dimeric twofold-bridged [Ge ] cluster compound, with the exo-bonded phosphine substituent being involved in the cluster bridging. In case of the presence of sterically more demanding phosphines in [Ge {Si(TMS) } PR ] [R: Mes (3) and NiPr (4)], reactions with NHC CuCl yielded the complexes NHC Cu[η -Ge {Si(TMS) } (PR )] [R: Mes (5) and NiPr (6)], comprising exclusively Cu-Ge bonds. Compounds 5 and 6 show varying reactivity in dependence of the identity of the phosphine group and represent the first examples of fourfold-substituted [Ge ] clusters with three different ligands bound to the [Ge ] cluster core. All compounds were characterized by H, C, P, and Si NMR spectroscopy. Additionally, compounds 3 and 4 were analyzed by ESI-MS, and the structures of compounds 1, 2, and 5 were characterized by single-crystal X-ray diffraction.

Section: Introductionmentioning

confidence: 99%

On the Variable Reactivity of Phosphine‐Functionalized [Ge₉] Clusters: Zintl Cluster‐Substituted Phosphines or Phosphine‐Substituted Zintl Clusters

Geitner

Wallach

Fässler

2018

“…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 . Selected members include a diatomic dumbbell in [Pd 2 @E 18 ] 4− (E=Ge, Sn), [M 2 @Sn 17 ] x − (M=Ni, Pt, Co), and [Ni 2 Sn 7 Bi 5 ] 3− , a trimeric filament in [Ni 3 @Ge 18 ] 4− , an Au 3 triangle in [Au 3 Ge 18 ] 5− , and a Pd 3 triangle in [Pd 3 Sn 8 Bi 6 ] 4− .…”

Section: Introductionmentioning

confidence: 99%

“…Selected members include a diatomic dumbbell in [Pd 2 @E 18 ] 4− (E=Ge, Sn), [M 2 @Sn 17 ] x − (M=Ni, Pt, Co), and [Ni 2 Sn 7 Bi 5 ] 3− , a trimeric filament in [Ni 3 @Ge 18 ] 4− , an Au 3 triangle in [Au 3 Ge 18 ] 5− , and a Pd 3 triangle in [Pd 3 Sn 8 Bi 6 ] 4− . A recently reported ligand‐stabilized Ge 18 cage, namely [Pd 3 @Ge 18 (Sn i Pr 3 ) 6 ] 2− , was observed to enclose a similar Pd 3 triangle. Its structure can also be viewed as a face‐fused dimer of an icosahedron through the common Pd 3 triangle.…”

Section: Introductionmentioning

confidence: 99%

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

Liu

Popov

et al. 2017

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.

“…Another derivatization of Ge 9 4− using a Pd complex was published by Sevov and co‐workers . Here, the Ge 9 4− moiety is first transferred into its [Ge 9 (Sn i Pr 3 ) 3 ] − derivative by attachment of three tris‐isopropyltin units.…”

Section: Formation Of Ligand‐free Metal Clustersmentioning

confidence: 99%

“… Molecular structure of the “twinned icosahedron” cluster anion [Pd 3 {Ge 9 (Sn i Pr 3 ) 3 } 2 ] 2− . Ge: red, Sn: orange, Pd: grey, organic groups at Sn are omitted for clarity.…”

Section: Formation Of Ligand‐free Metal Clustersmentioning

confidence: 99%

(Multi‐)Metallic Cluster Growth

Weinert

Mitzinger

Dehnen

2018

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.