[Si(SiMe3)3]6Ge18M (M = Zn, Cd, Hg): neutral metalloid cluster compounds of germanium as highly soluble building blocks for supramolecular chemistry

Abstract

Very recently it was shown that the metalloid cluster compound {Ge(9)[Si(SiMe(3))(3)](3)}(-) can be used for subsequent reactions as the shielding of the cluster core is rather incomplete. So the reaction of with M(+) sources of group 11 metals gives metalloid cluster compounds of the formulae {MGe(18)[Si(SiMe(3))(3)](6)}(-) (M = Au, Ag, Cu). These reactions can be seen as first steps into a supramolecular chemistry with metalloid cluster compounds. However, further build-up reactions lead to insoluble products, thus better soluble starting materials are needed for further build-up reactions. Here the first neutral MGe(18)[Si(SiMe(3))(3)](6) (M = Hg, Cd, Zn) compounds are described, exhibiting a strongly enhanced solubility in inert solvents. Beside the synthesis, the structural properties as well as the bonding situations in these cluster compounds are discussed.

Metalloid Cluster Compounds of Group 14: Bonding Properties and Subsequent Reactions

“…This primary goal is achieved by the synthesis of neutral MGe 18 [Si(SiMe 3 ) 3 ] 6 cluster compounds (M = Zn, Cd, Hg). 15 From these neutral compounds, which are easily dissolved even in pentane, further build-up reactions might lead to larger soluble compounds. Thereby neutral linkers, e.g., metal atoms such as Ni, Pd, or Pt, leading again to neutral compounds, would be most interesting.…”

[Ge12{FeCp(CO)2}8{FeCp(CO)}2]: A Ge12 Core Resembles the Arrangement of the High‐Pressure Modification Germanium (II)

“…This shows that the influence of transition-metal ligands on metalloid clusters is nearly unexplored. Furthermore, such metalloid clusters stabilized with transition-metal-based ligands might open an access to new metastable binary materials.[15] However, transitionmetal reagents have already been used in the chemistry of germanium clusters; either as ligands in direct synthesis to gain fully substituted clusters, such as [Ge 6 {Cr(CO) 5 X compounds (X = À1: M = Cu, Ag, Au;[23, 24] X = 0: M = Zn, Cd, Hg [25] ). We now present a second example of a metalloid maingroup cluster exclusively stabilized by transition-metal-based ligands, showing a unique arrangement of the tetrel atoms in the cluster core.…”

Metal‐Centered Zintl Ions Isolated by Direct Extraction from Endohedral Intermetallic Precursor: [Co1–x@Sn9]4– (x ≈ 0.32) and [Co2@Sn17]5–

“…[22] Clusters including elements of groups 8 and 9 are less frequent and also the number of observed arrangements decreases: [Ge 8 Fe (CO) 3 ] 3-, [23] heavily disordered deltahedra [Fe@Sn 10 ] 3-, [24] [Ru@Ge 12 ] 3-with D 2h symmetry, [25] two analogues of pentagonal prismatic cage [Fe@Ge 10 ] 3- [26] and [Co@Ge 10 ] 3-, [5] more compounds such as monomer [Co@Sn 9 ] 5-, [27] cluster dimers [Co 2 @Sn 17 ] 5-, [27] as well as [Ir@Sn 12 ] 3-, [28] which is made from coordinated heteroatoms [Sn 9 Ir(cod)] 3-. [28] Aside from the mentioned examples with d-block elements, metal-centered clusters have only rarely been reported: 36-electron closed-shell icosahedral [Mn@Pb 12 ] 3-, [29] [Cu@Pb 9 ] 3-, [30] and [Cu@Sn 9 ] 3-with different C 4v /D 3h arrangement, [30] clusters with embedded metal atoms like the half-centered-half-capped [(η 4 -Sn 8 )Ti(Cp)] [34] closo-[E 9 ZnR] 3-(E = Si, Ge, Sn, Pb; R = Mes, iPr, Ph), [35] [E 9 3-, [36] [Ge 9 Cu(PR 3 )]…”