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We report the synthesis and characterization of ionic compounds [(thf)4YbI]2[Ge9(Hyp)3]2 (1) and [(thf)5LnI]4[Ge9(Hyp)3]4 (Ln = Eu (2), Sm (3)), (Hyp = Si(SiMe3)3). All compounds were examined by UV-Vis spectroscopy and a blue luminescence of Eu2+ was found. The solid state magnetic measurements of complexes 2 and 3 confirmed the presence of divalent lanthanides. [ABSTRACT FROM AUTHOR]

We present a series of new intermetalloid clusters (R3P)CuGe9((Hyp)3, (R=Me, Et, iPr, nBu, tBu) (Hyp=Si(SiMe3)3) (R3P)AuGe9(Hyp)3MGe9(Hyp)3 (R=Ph, Me; M=Au, Cu). In conjunction with already known clusters, these give new insights into the bonding situation of metal bridged Ge9 clusters as well as a better understanding of the formation of these clusters. Additionally, the intermetalloid clusters with the smallest phosphine PMe3 show new bonding motives. [ABSTRACT FROM AUTHOR]

Within the reaction of a metastable Ge(I)Cl solution and Na2Fe2(CO)8 the anionic cubic cluster compound {(thf)14Na6Ge8[Fe(CO)4]8}− (3) is obtained. The open shell character of 3 is proven by EPR spectroscopy. Quantum chemical calculations furthermore show that also the closed shell systems should be stable, but could not be isolated so far. Additionally, 3 can be seen as an intermediate cluster compound on the formation of metalloid clusters. [ABSTRACT FROM AUTHOR]

The reaction of a metastable SnCl solution with KR (R = Si(SiMe3)2(SitBuMe2) = HyptBuMe2 or Si(SiMe3)2(SiEt3) = HypEt3) gives the metalloid tin cluster [Sn10R4]2− in partly good yields. The tin clusters are in the solid state as well in solution coordinated by a potassium cation, leading first of all to a more static compound and novel coordination polymers in the solid state. Additionally, the coordination of the potassium cation strongly increases the stability of the cluster in solution. This higher stability is thereby an important prerequisite for future investigation of this open shell metalloid tin cluster. [ABSTRACT FROM AUTHOR]

We present a series of new intermetalloid clusters (R3P)CuGe9((Hyp)3, (R=Me, Et, iPr, nBu, tBu) (Hyp=Si(SiMe3)3) (R3P)AuGe9(Hyp)3MGe9(Hyp)3 (R=Ph, Me; M=Au, Cu). In conjunction with already known clusters, these give new insights into the bonding situation of metal bridged Ge9 clusters as well as a better understanding of the formation of these clusters. Additionally, the intermetalloid clusters with the smallest phosphine PMe3 show new bonding motives. [ABSTRACT FROM AUTHOR]

The ligands used for the protection of metalloid clusters heavily influence the resulting structure and shape. For silver, thiolate and alkynyl ligands are commonly used, while phosphines usually play a minor role as co-ligands. Herein, we report the synthesis and structural characterization of Ag108(PEt3)24Cl6 (1), the largest structurally characterized metalloid silver cluster with phosphines and halides as sole ligands. Instead of the frequently observed spherical shape of metalloid clusters, 1's structure resembles a hexagonal prism. The highly light and temperature sensitive compound features many similarities to its smaller congener Ag64(PnBu3)16Cl6, though there are distinct structural and electronic differences present. Within 1, a Ag64 subunit can be found, which identifies these clusters as molecular seeds for the formation of faceted nanoparticles., (© 2024 Wiley‐VCH GmbH.)

We report the synthesis of three neutral complexes with different coordination modes of a di-silylated metalloid germanium cluster to divalent lanthanides [(thf) 5 Ln(η n -Ge 9 (Hyp) 2 )] (Ln = Yb ( 1 , n = 1); Eu ( 2 , n = 2, 3), Sm ( 3 , n = 2, 3); Hyp = Si(SiMe 3 ) 3 ) by the salt metathesis of LnI 2 with K 2 [Ge 9 (Hyp) 2 ] in THF. The complexes were characterized by elemental analysis, nuclear magnetic resonance and UV-vis-NIR spectroscopy, and single-crystal X-ray diffraction. In thf solution, the formation of contact or solvate-separated ion pairs depending on the concentration is assumed. Compound 2 exhibits a blue luminescence typical for Eu 2+ . The solid-state magnetic measurements of compounds 2 and 3 confirm the presence of divalent europium and samarium, respectively.

We report the reactions of K 2 [Ge 9 (Hyp) 2 ] (Hyp = Si(SiMe 3 ) 3 ) with (thf) 3 YbI 3 , ThI 4 , and UCl 4 , leading to the oxidative coupling of the metalloid germanium cluster to form the dimeric dianion [Ge 18 (Hyp) 4 ] 2- . The novel dimerized Ge 18 -cluster was isolated and characterized by single-crystal X-ray diffraction analysis as a component of ionic compounds [Yb(thf) 6 ][Ge 18 (Hyp) 4 ] ( 1 ) and [K(2.2.2-crypt)] 2 [Ge 18 (Hyp) 4 ] ( 2 ) with two different counterions. The dihedral angle between two intact Ge 9 cages depends on the counterions, which was also studied by quantum-chemical calculations.

The oxidation of K[Ge 9 (Hyp) 3 ] (Hyp = Si(SiMe 3 ) 3 ) with lanthanide triiodides LnI 3 (Ln = Eu, Sm, Yb) leads to the formation of novel clusters with a Ge 18 -core isolated as a co-crystallizate of Ge* 18 (Hyp) 6 ( 1a ) and Ge 18 (Hyp) 5 (Si(SiMe 3 ) 2 )(SiMe 3 ) ( 1b ). Clusters 1a and 1b differ distinctly from the known cluster Ge 18 (Hyp) 6 ( A ), which has been found earlier in the reaction of K[Ge 9 (Hyp) 3 ] with FeCl 2 and now identified as an intermediate product in the production of compounds 1a and 1b . These three compounds A , 1a , and 1b are thus structural isomers being the first example of genuine isomerism in metalloid main-group cluster compounds.

Within the reaction of a metastable Ge(I)Cl solution and Na 2 Fe 2 (CO) 8 the anionic cubic cluster compound {(thf) 14 Na 6 Ge 8 [Fe(CO) 4 ] 8 } - (3) is obtained. The open shell character of 3 is proven by EPR spectroscopy. Quantum chemical calculations furthermore show that also the closed shell systems should be stable, but could not be isolated so far. Additionally, 3 can be seen as an intermediate cluster compound on the formation of metalloid clusters.