The reaction of GeBr with LiSi(SiMe(3))(3) leads to the metalloid cluster compound [(THF)(2)Li](3)Ge(14)[Si(SiMe(3))(3)](5) (1). After the introduction of a first cluster of this type, in which 14 germanium atoms form an empty polyhedron, [(THF)(2)Li](3)Ge(14)[Ge(SiMe(3))(3)](5) (2), we present here further investigations on 1 to obtain preliminary insight into its chemical and bonding properties. The molecular structure of 1 is determined via X-ray crystal structure solution using synchrotron radiation. The electronic structure of the Ge(14) polyhedron is further examined by quantum chemical calculations, which indicate that three singlet biradicaloid entities formally combine to yield the singlet hexaradicaloid character of 1. Moreover, the initial reactions of 1 after elimination of the [Li(THF)(2)](+) groups by chelating ligands (e.g., TMEDA or 12-crown-4) are presented. Collision induced dissociation experiments in the gas phase, employing FT-ICR mass spectrometry, lead to the elimination of the singlet biradicaloid Ge(5)H(2)[Si(SiMe(3))(3)](2) cluster. The unique multiradicaloid bonding character of the metalloid cluster 1 might be used as a model for reactions and properties in the field of surface science and nanotechnology.
Single‐crystalline K+, Rb+, and Cs+ salts of the ortho‐tellurostannate anion have been prepared by a very efficient fusing/extraction/evaporation method. The resulting compounds with the general composition [A4(H2O)n][SnTe4] can be transferred into mixed H2O/en solvates by solving the hydrates in 1,2‐diaminoethane (en) and ensuing layering by toluene. A mixed Rb+/Ba2+ salt results from a partial cation exchange of the Rb+ hydrate phase in solution. All hydrates react to polytellurides when exposed to air and represent useful starting materials for the synthesis of transition metal complexes with [SnTe4]4− groups as binary main group elemental ligands. [K4(H2O)0.5][SnTe4] (1), [Rb4(H2O)2][SnTe4] (2), [Cs4(H2O)2][SnTe4] (3), [K4(H2O)(en)][SnTe4] (4), [Rb4(H2O)0.67(en)0.33][SnTe4] (5), [Cs4(H2O)0.5(en)0.5][SnTe4] (6), and [Rb2Ba(H2O)11][SnTe4] (7) were characterized by means of X‐ray diffractometry and optical absorption spectroscopy.
Alkaline earth metal derivatives of the diphosphanyldisiloxane O(SiiPr 2 PH 2 ) 2 (1) were obtained by reactions of 1 with MgBu 2 and M{N(SiMe 3 ) 2 } 2 (M = Ca, Sr, Ba), respectively. The metal complexes formed were characterised by elemental analysis, NMR spectroscopy, and IR spectroscopy as well as by single-crystal structure analysis. The solid-state structures depend on the metal ion involved. The magnesium derivative crystallizes from thf as a trimer and exhibits a six-mem-
The synthesis of siloxane-bridged P 2 and P 4 compounds can be achieved through metalation of primary or cyclic diphosphanylsiloxane compounds and subsequent oxidative coupling using C 2 H 4 Br 2 as reagent. Starting from the cyclic diphosphanylsiloxane [O(iPr 2 Si) 2 PH] 2 , the reaction with the silazanides of the earth alkaline metals leads to the metalated compounds [M(DME) 2 {O(iPr 2 Si) 2 P} 2 ] (1: M = Ca, 2: M = Sr, 3: M = Ba). Subsequent oxidation yields the bicyclic species
Two new hybrid ligands that exhibit organic as well as siloxane chains between four phosphorus atoms in bridge-head positions were synthesized. These species show a very different ability with regard to the formation of coordination compounds. Whereas compound 1 with the short (C 2 H 4 ) 2 O ether units shows no ability to act as a ligand, the compound with the longer (C 2 H 4 O) 2 C 2 H 4 chains between the siloxane[a]
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