2012
DOI: 10.1021/ja304251t
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Soluble Zintl Phases A14ZnGe16 (A = K, Rb) Featuring [(η3-Ge4)Zn(η2-Ge4)]6– and [Ge4]4– Clusters and the Isolation of [(MesCu)233-Ge4)]4–: The Missing Link in the Solution Chemistry of Tetrahedral Group 14 Element Zintl Clusters

Abstract: The number of Zintl phases containing polyhedral clusters of tetrel elements that are accessible for chemical reactions of the main-group element clusters is rather limited. The synthesis and structural characterization of two novel ternary intermetallic phases A(14)ZnGe(16) (A = K, Rb) are presented, and their chemical reactivity is investigated. The compounds can be rationalized as Zintl phases with 14 alkali metal cations A(+) (A = K, Rb), two tetrahedral [Ge(4)](4-) Zintl anions, and one anionic heterometa… Show more

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Cited by 50 publications
(42 citation statements)
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“…[6][7][8] The E1-E4 bond [2.702(2) Å; highlighted in light grey in Figure 3] is 4-matches with x = 2.2(1) within standard deviations (3σ limit) the values of the precursor phase NaRb 7 (Si 2 Ge 2 ) 2 . A small change in the E-E bond length compared with homoatomic Si 4 or Ge 4 clusters is visible in 2a, while a change of positional or anisotropic displacement parameters is not noticeable from the comparative picture illustrated in Figure S5 in the Supporting Information.…”
Section: Reactivity Of Narb 7 (Si 4-x Ge X ) 2 In Liquid Ammoniamentioning
confidence: 82%
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“…[6][7][8] The E1-E4 bond [2.702(2) Å; highlighted in light grey in Figure 3] is 4-matches with x = 2.2(1) within standard deviations (3σ limit) the values of the precursor phase NaRb 7 (Si 2 Ge 2 ) 2 . A small change in the E-E bond length compared with homoatomic Si 4 or Ge 4 clusters is visible in 2a, while a change of positional or anisotropic displacement parameters is not noticeable from the comparative picture illustrated in Figure S5 in the Supporting Information.…”
Section: Reactivity Of Narb 7 (Si 4-x Ge X ) 2 In Liquid Ammoniamentioning
confidence: 82%
“…Therefore, an ammonia solution of NaRb 7 (Si 2 Ge 2 ) 2 was treated with 18-crown-6 and MesCu. 4-(x = 0, 0.7, 4) [6][7][8] (2a, Figure 3 (3), [6] however with less NH 3 solvate molecules.…”
Section: Reactivity Of Narb 7 (Si 4-x Ge X ) 2 In Liquid Ammoniamentioning
confidence: 99%
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“…In the case of the clusters of the heavier homologues Sn and Pb, the migration of Cu + into the polyhedral clusters under the loss of the original ligand sphere and formation of the endohedrally filled [Cu@E 9 ] 3− (E = Sn, Pb) clusters was observed for CuMes [8]. By contrast, the reaction of CuMes with the smaller tetrahedral Zintl clusters [E 4 ] 4− leads to the mesitylcopper complexes [(MesCu) 2 (η 3 -E 4 )] 4− (E = Si, Ge) [9,10]. Additionally, larger intermetalloids [Au 3 Ge 18 ] 5− and [Au 3 Ge 45 ] 4− were obtained in the reaction of bare [Ge 9 ] 4− clusters with (PPh 3 )AuCl [11,12].…”
Section: Introductionmentioning
confidence: 99%