Reaction of GeCl 2 ‚dioxane with 2 equiv of Li(THF) 2.5 Ge(SiMe 3 ) 3 in hexane afforded moderate yields of two cyclopolygermanes. A cyclotrigermane, (Ge(SiMe 3 ) 2 ) 3 , was characterized by NMR spectra, elemental analyses, and an X-ray crystal structure determination. It crystallized from pentane in the R3 hc space group (rhombohedral) with a ) 19.294(3) Å, R ) 31.89(1)°, V ) 1781 Å 3 , and Z ) 2. The Ge 3 core consisted of an equilateral triangle with a Ge-Ge distance of 2.460(1) Å, the shortest so far measured in cyclotrigermanes. The second product was tentatively identified by its NMR spectra as a cyclotetragermane, ((Me 3 Si) 3 GeGeCl) 4 , and this was confirmed by elemental analyses and an X-ray structure determination on the yellow crystals formed from pentane. The product was found to crystallize as a complex with two molecules of Ge(SiMe 3 ) 4 in the F2 3 (cubic) space group with a ) 22.7731(3) Å, V ) 11 810.5 Å 3 , and Z ) 8. The Ge 4 core consisted of a nonplanar four-membered ring (fold angle ) 18.7°) disordered over three positions related by 3-fold symmetry. In the assumed ordered structure, ring Ge-Ge distances averaged 2.503 Å. When the reaction was repeated with GeCl 2 ‚dioxane and 2 equiv of Li(THF) 3 Si(SiMe 3 ) 3 , the known disilagermirane, (Me 3 Si) 2 Ge(Si(SiMe 3 ) 2 ) 2 , was isolated (66% yield) along with a small yield of the known cyclotetragermane, ((Me 3 Si) 3 SiGeCl) 4 . Reaction of GeI 2 with Li(THF) 2.5 Ge(SiMe 3 ) 3 gave only traces of the cyclotrigermane.
Professor Hansgeorg Schno È ckel zum 60. Geburtstag gewidmet Inhaltsu È bersicht. Durch Natriumhalogenidabspaltung bei der Reaktion von Indium(III)-halogeniden mit Natrium-tri-tertbutoxistannat(II) bzw. Natrium-tri-tert-butoxigermanat(II) gelang die Synthese dreier neuer heterometallischer und heteroleptischer Alkoxoverbindungen THF´Cl 2 In(OtBu) 3 Sn (1), THF´Br 2 In(OtBu) 3 Sn (2) und THF´Cl 2 In(OtBu) 3 Ge (3). Die Moleku È lstrukturen von 1 und 2 im Festko È rper konnten aus Einkristallro È ntgenstrukturanalysen bestimmt werden, wa È hrend das dynamische Verhalten der Moleku È le in Lo Èsung aus temperaturabha È ngigen NMR-Spektren folgt. Die Kristallstrukturen der Verbindungen 1 und 2 sind, abgesehen von den unterschiedlichen Halogenatomen, a È hnlich und isostrukturell. Beide kristallisieren im orthorhombischen Kristallsystem in der Raumgruppe Pbca mit acht Moleku È len pro Elementarzelle. Die Schwermetallatome befinden sich auf den apikalen Positionen einer trigonalen Bipyramide mit angena È herter Punktsymmetrie C s (m) und sind u È ber Sauerstoffatome miteinander verknu È pft, welche die a È quatorialen Positionen der Bipyramide einnehmen. Die Indiumatome haben in beiden Verbindungen eine verzerrt oktaedrische Koor-dination aus 4 Sauerstoff-und zwei Halogenatomen, wohingegen die Zinnatome trigonal pyramidal von Sauerstoffatomen koordiniert sind. Trotz der asymmetrischen Koordination durch die THF-Basen an den Indiumatomen findet man sehr einfache NMR-Spektren in Lo È sung, die erst bei tieferen Temperaturen komplexer werden. Tri(tert-butoxi)indium [In(OtBu) 3 ] 2 (4), wird durch Alkoholyse von In(N(Si(CH 3 ) 3 ) 2 ) 3 mit tert-Butanol in Toluen hergestellt und aus Hexan kristallisiert. Mit Hilfe einer Einkristallro È ntgenstrukturanalyse von 4 gelang erstmals die Aufkla È rung der Struktur eines homometallischen, homoleptischen Indiumalkoxides. Verbindung 4 kristallisiert im monoklinen Kristallsystem mit acht dimeren Einheiten pro Elementarzelle in der Raumgruppe C2/c. Die dimere Einheit hat C 2 -Symmetrie und einen nahezu planaren zentralen In 2 O 2 -Ring, welcher durch die Verbru È ckung der Indiumatome durch Alkoxogruppen gebildet wird. Durch die Dimerisierung erhalten die Schwermetallatome vier Sauerstoffliganden in verzerrt tetraedrischer Umgebung.Abstract. Through sodium halide elimination between Indium(III) halides and sodium-tri-tert-butoxistannate(II) or sodium-tri-tert-butoxigermanate(II) the three new heterometallic and heteroleptic alkoxo compounds THF´Cl 2 In-(OtBu) 3 Sn (1), THF´Br 2 In(OtBu) 3 Sn (2), and THF´Cl 2 In-(OtBu) 3 Ge (3), have been synthesized. The molecular structures of 1 and 2 in the solid state follow from single crystal X-ray structure determinations while structural changes in solution may be derived from temperature dependant NMR spectroscopy. The crystal structures of compounds 1 and 2 are despite different halide atoms isostructural. Both crystallize in the ortho-rhombic crystal system in space group Pbca with eight molecules per unit cell. The heavy atoms occupy the ...
Reaction of SnCl(2).dioxane with 2 equiv of Li(THF)(3)Si(SiMe(3))(3) in hexane afforded the cyclotetrastannane [(Me(3)Si)(3)SiSnCl](4) in reasonable yield. From pentane, the product crystallized as a red-orange disolvate in the P&onemacr; space group (triclinic) with a = 14.735(2) Å, b = 14.976(2) Å, c = 24.066(3) Å, alpha = 76.94 degrees, beta = 76.19 degrees, gamma = 62.11 degrees, V = 4517.5 Å(3), and Z = 2. The Sn(4) ring consisted of a slightly distorted, nonplanar (fold angle = 18.9 degrees ) rectangle with Sn-Sn distances of 2.8054(6), 2.8111(6), 2.9122(6), and 2.9146(6) Å. The pentane molecules were disordered. Selected mono- and dihalogermanes were treated with 1 equiv of Li(THF)(3)Si(SiMe(3))(3) or Li(THF)(2.5)Ge(SiMe(3))(3), affording (Me(3)Si)(3)EGe(CF(3))(3) (E = Si, Ge) and (Me(3)Si)(3)GeGeR(3) (R = Cl, CH(3), C(6)H(5)). Besides the monosubstitution product, the reaction of GeCl(4) with 1 equiv of Li(THF)(2.5)Ge(SiMe(3))(3) also gave a small amount of the linear tetragermane (Me(3)Si)(3)GeGeCl(2)GeCl(2)Ge(SiMe(3))(3). Good yields of the analogous phenyl derivative, (Me(3)Si)(3)GeGePh(2)GePh(2)Ge(SiMe(3))(3), were obtained by treating Ph(2)GeCl(2) with 2 equiv of the lithium-germyl reagent.
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