2,2,3,3,5,5,6,6-Octa-p-tolyl-1,4-dioxa-2,3,5,6-tetra­germacyclo­hexane dichloro­methane disolvate

The title compound, C56H56Ge4O2·2CH2Cl2 or Tol8Ge4O2·2CH2Cl2 (Tol = p-CH3C6H4), was obtained serendipitously during the attempted synthesis of a branched oligogermane from Tol3GeNMe2 and PhGeH3. The mol­ecule contains an inversion center in the middle of the Ge4O2 ring which is in a chair conformation. The Ge—Ge bond distance is 2.4418 (5) Å and the Ge—O bond distances are 1.790 (2) and 1.785 (2) Å. The torsion angles within the Ge4O2 ring are −56.7 (1) and 56.1 (1)° for the Ge—Ge—O—Ge angles and −43.9 (1)° for the O—Ge—Ge—O angle

Synthetic, Structural, and Physical Investigations of the Large Linear and Branched Oligogermanes Ph₃GeGePh₂GePh₂GePh₂H, Ge₅Ph₁₂, and (Ph₃Ge)₄Ge

The syntheses of two linear oligogermanes, Ph₃GeGePh₂GePh₂GePh₂H and Ge₅Ph₁₂, were achieved using a hydrogermolysis reaction starting with HPh₂GeGePh₂GePh₂H. The preparation of the hydride-terminated tetragermane indicates that selectivity is possible using the hydrogermolysis reaction, which had not been observed previously. The structures of both of these compounds were determined, and they were also characterized by UV/visible spectroscopy and electrochemical methods (CV and DPV). The pentagermane Ge₅Ph₁₂ exhibits four irreversible oxidation waves in both its CV and DPV, as was observed for other aryl-substituted oligogermanes. The successful synthesis of the neopentane analogue (Ph₃Ge)₄Ge was also achieved by starting from GeH₄ and Ph₃GeCH₂CN. This material was structurally characterized; the structure of (Ph₃Ge)₄Ge is highly sterically congested and contains long Ge–Ge single-bond distances that average 2.497(6) Å and exhibits an nearly idealized tetrahedral geometry at the central germanium atom with an average Ge–Ge–Ge bond angle of 109.49(2)°. The UV/visible spectrum of (Ph₃Ge)₄Ge exhibits a broad absorbance maximum centered at 250 nm, and DFT calculations indicate that this compound has a stabilized HOMO at −6.223 eV and a large HOMO–LUMO gap relative to those in other branched oligogermanes

Synthetic, Structural, and Physical Investigations of the Large Linear and Branched Oligogermanes Ph₃GeGePh₂GePh₂GePh₂H, Ge₅Ph₁₂, and (Ph₃Ge)₄Ge

The syntheses of two linear oligogermanes, Ph₃GeGePh₂GePh₂GePh₂H and Ge₅Ph₁₂, were achieved using a hydrogermolysis reaction starting with HPh₂GeGePh₂GePh₂H. The preparation of the hydride-terminated tetragermane indicates that selectivity is possible using the hydrogermolysis reaction, which had not been observed previously. The structures of both of these compounds were determined, and they were also characterized by UV/visible spectroscopy and electrochemical methods (CV and DPV). The pentagermane Ge₅Ph₁₂ exhibits four irreversible oxidation waves in both its CV and DPV, as was observed for other aryl-substituted oligogermanes. The successful synthesis of the neopentane analogue (Ph₃Ge)₄Ge was also achieved by starting from GeH₄ and Ph₃GeCH₂CN. This material was structurally characterized; the structure of (Ph₃Ge)₄Ge is highly sterically congested and contains long Ge–Ge single-bond distances that average 2.497(6) Å and exhibits an nearly idealized tetrahedral geometry at the central germanium atom with an average Ge–Ge–Ge bond angle of 109.49(2)°. The UV/visible spectrum of (Ph₃Ge)₄Ge exhibits a broad absorbance maximum centered at 250 nm, and DFT calculations indicate that this compound has a stabilized HOMO at −6.223 eV and a large HOMO–LUMO gap relative to those in other branched oligogermanes

Synthetic, Structural, and Physical Investigations of the Large Linear and Branched Oligogermanes Ph₃GeGePh₂GePh₂GePh₂H, Ge₅Ph₁₂, and (Ph₃Ge)₄Ge

The syntheses of two linear oligogermanes, Ph₃GeGePh₂GePh₂GePh₂H and Ge₅Ph₁₂, were achieved using a hydrogermolysis reaction starting with HPh₂GeGePh₂GePh₂H. The preparation of the hydride-terminated tetragermane indicates that selectivity is possible using the hydrogermolysis reaction, which had not been observed previously. The structures of both of these compounds were determined, and they were also characterized by UV/visible spectroscopy and electrochemical methods (CV and DPV). The pentagermane Ge₅Ph₁₂ exhibits four irreversible oxidation waves in both its CV and DPV, as was observed for other aryl-substituted oligogermanes. The successful synthesis of the neopentane analogue (Ph₃Ge)₄Ge was also achieved by starting from GeH₄ and Ph₃GeCH₂CN. This material was structurally characterized; the structure of (Ph₃Ge)₄Ge is highly sterically congested and contains long Ge–Ge single-bond distances that average 2.497(6) Å and exhibits an nearly idealized tetrahedral geometry at the central germanium atom with an average Ge–Ge–Ge bond angle of 109.49(2)°. The UV/visible spectrum of (Ph₃Ge)₄Ge exhibits a broad absorbance maximum centered at 250 nm, and DFT calculations indicate that this compound has a stabilized HOMO at −6.223 eV and a large HOMO–LUMO gap relative to those in other branched oligogermanes

Synthetic, Structural, and Physical Investigations of the Large Linear and Branched Oligogermanes Ph₃GeGePh₂GePh₂GePh₂H, Ge₅Ph₁₂, and (Ph₃Ge)₄Ge

The syntheses of two linear oligogermanes, Ph₃GeGePh₂GePh₂GePh₂H and Ge₅Ph₁₂, were achieved using a hydrogermolysis reaction starting with HPh₂GeGePh₂GePh₂H. The preparation of the hydride-terminated tetragermane indicates that selectivity is possible using the hydrogermolysis reaction, which had not been observed previously. The structures of both of these compounds were determined, and they were also characterized by UV/visible spectroscopy and electrochemical methods (CV and DPV). The pentagermane Ge₅Ph₁₂ exhibits four irreversible oxidation waves in both its CV and DPV, as was observed for other aryl-substituted oligogermanes. The successful synthesis of the neopentane analogue (Ph₃Ge)₄Ge was also achieved by starting from GeH₄ and Ph₃GeCH₂CN. This material was structurally characterized; the structure of (Ph₃Ge)₄Ge is highly sterically congested and contains long Ge–Ge single-bond distances that average 2.497(6) Å and exhibits an nearly idealized tetrahedral geometry at the central germanium atom with an average Ge–Ge–Ge bond angle of 109.49(2)°. The UV/visible spectrum of (Ph₃Ge)₄Ge exhibits a broad absorbance maximum centered at 250 nm, and DFT calculations indicate that this compound has a stabilized HOMO at −6.223 eV and a large HOMO–LUMO gap relative to those in other branched oligogermanes