Germanium/phosphorus cage compounds with germanium in three different oxidation states

Almstätter, Stefan; Baláȥs, Gábor; Bodensteiner, Michael; Scheer, Manfred

doi:10.1039/c1cc13937a

Cited by 12 publications

(9 citation statements)

References 42 publications

(7 reference statements)

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“…The isolated compounds are almost insoluble, however, which might be the driving force of their formation. Nevertheless, this method seems to be the way to obtain unprecedented mixed‐valence cage compounds 5b. Due to their insolubility, a spectroscopic characterization of the products in solution was not possible, but elemental analysis and X‐ray diffraction reveal clearly the composition of the new products.…”

Section: Resultsmentioning

confidence: 99%

“…In contrast, we focused on the use of the monolithiated species Li t BuPH. First investigations towards the reactions with GeCl 2 led to the novel mixed‐valence cage compounds F and G 5b. By applying this procedure to the heavier group 14 metal halides of tin and lead, we were now able to synthesize first derivatives of type B and C containing lead as a metal.…”

Section: Introductionmentioning

confidence: 99%

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Cage Compounds of Phosphorus and the Heavier Group 14 Elements

Almstätter

Eberl

Baláȥs

et al. 2012

Zeitschrift anorg allge chemie

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The Sn/P cage compounds [Sn 10 (tBuP) 4 ] (1) and [Sn 10 (tBuP) 7 Cl 4 ] (2) were obtained by the reaction of LitBuPH with SnBr 2 and SnCl 2 , respectively. Theoretical calculations confirm that the tin atoms in 2 feature different formal oxidation states. The reaction of PbCl 2 with LitBuPH and LiPHSiiPr 3 yields the Pb/P cage com-* Prof. Dr. M. Scheer 1739 pounds [Pb 7 (tBuP) 7 ] (3) and [Pb 6 (PSiiPr 3 ) 6 ] (4), respectively, that represent new derivatives of known polyhedrons of this class of compounds. The new products were characterized by X-ray diffraction, elemental analysis and partially by MS and MAS-NMR spectroscopy.nations of Sn/P [3] and Pb/P. [4] For the latter only few examples exist, which is also true for corresponding Ge/P systems. [5] Depending on the used synthetic method and steric requirements of the adjacent substituents, different polyhedrons are obtained. Usually, cubes and hexagonal prismatic structures dominate as shown in type A and B compounds for M 4 (PR) 4 and M 6 (PR) 6 derivatives. For the composition M 7 (PR) 7 compounds of type C are known, whereas by using a thermal condensation reaction of R 2 Ge(PH 2 ) 2 compound D was synthesized. [6] A first mixed valence cage E was obtained by von Hänisch et al. by the reaction of SnCl 2 with Li 2 P(SiPr 3 ). [7] Published synthetic procedures involve reactions between RPH 2 or LiHPR and e.g. Sn(NMe 2 ) 2 [3,8] or LiCl elimination reactions that use the double lithiated species RPLi 2 and dihal-M. Scheer et al.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Cage Compounds of Phosphorus and the Heavier Group 14 Elements

Almstätter

Eberl

Baláȥs

et al. 2012

Zeitschrift anorg allge chemie

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“…The structure of the electron precise chloride [Ge 7 (P t Bu) 4 Cl 6 ] is presented in Figure b and shows a core made of six five‐membered rings and is therefore structurally similar to the ufosane structure of P 11 3− in Na 3 P 11 . The Ge 8 P 4 cage in the bromide contains six five‐membered rings and one four‐membered ring …”

Section: Divalent Halides Of Germanium Tin and Leadmentioning

confidence: 98%

“…[41] The Ge 8 P 4 cage in the bromide contains six five-membered rings and one four-membered ring. [42] Germanium diiodide is synthesized by the reaction of germaniumt etraiodide with H 3 PO 2 and is isostructuralt oC dI 2 . [43] Huttner and co-workers showed, that the reaction of germanium diiodide with the transition-metal-based compound Na 2 [Cr 2 (CO) 10 ]i nt he presence of 2,2'-bipyridine leads to the anionic cluster[ {(CO) 5 Cr} 6 Ge 6 ] 2À with an octahedrally shaped Ge 6 cluster core ( Figure 3c).…”

Section: Pbxmentioning

confidence: 99%

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Halides of the Heavier Group 14 Homologues Germanium, Tin, and Lead—A Journey through Unusual Compounds and Oxidation States

Kunz

Schnepf

2018

Chemistry A European J

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Classical halides of the heavier Group 14 homologues germanium, tin, and lead are common precursors for the synthesis of exciting compounds, such as polyhedral clusters. To get access to larger metalloid cluster compounds of Group 14, the disproportionation reaction of metastable monohalide solutions, accessible through a preparative co‐condensation reaction, proved to be quite successful. As the identity of the subvalent halides within the metastable solutions were yet unknown the reaction course from a monohalide precursor to a metalloid cluster was mostly unidentified. This might change now, as a first subhalide cluster [Ge14Br8(Et3P)4] could be characterized, being the first trapped intermediate of the disproportionation reaction of Group 14 subhalides. All these aspects are included within this Minireview, together with a short historical overview, dealing with the development of the preparative co‐condensation technique out of the matrix isolation technique, being the essential first step of the synthesis of metastable monohalide solutions of the heavier Group 14 elements Ge and Sn.

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X‐ray Crystallography of Organogermanium Compounds

Hemmert¹

2023

Organogermanium Compounds

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Germanium/phosphorus cage compounds with germanium in three different oxidation states

Abstract: Novel germanium/phosphorus cage compounds with new structural motifs have been synthesized containing germanium in three different oxidation states. The key to obtain this new class of compounds is the use of monolithiated primary phosphine LiHPtBu in the reaction with GeX 2 .

Cited by 12 publications

References 42 publications

Cage Compounds of Phosphorus and the Heavier Group 14 Elements

Cage Compounds of Phosphorus and the Heavier Group 14 Elements

Halides of the Heavier Group 14 Homologues Germanium, Tin, and Lead—A Journey through Unusual Compounds and Oxidation States

X‐ray Crystallography of Organogermanium Compounds

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