Digermoxane

Digermoxane, hexaphenyl-, formation of, by hydrolysis of tri-phenylbromogermane, 6 78 Dihydroxobis(diethyl sulfide)plati-num(II), 6 215... 

In 1952, West183 successfully used for the first time the reaction of R3GeX for the synthesis of (l-CioH7)3GeOH. The latter was so stable that it was transformed slowly and partially to the corresponding digermoxane only at 175 °C during 24 hours. 

We describe in detail the syntheses of digermoxane and its methyl analogues from the reaction of lead(II) oxide with bromogermanes. The procedures are convenient and well suited to large-scale preparations in a relatively short time (about 1 hr), using a minimum of special apparatus. The yields are in the range 87-98%. 

Caution. The digermoxanes are toxic and their exposure to air and/or moisture is likely to promote rapid decomposition. Manipulations should be... 

Digermoxane (vp4 about 66 torr at 0°) is a clear colorless liquid that is best stored at liquid nitrogen temperature in break-seal glass ampules. The 1H nmr spectrum,17 measured in cyclohexane, consists of a singlet [5(GeH)J at 5.28 ppm, while the infrared spectrum4 18 shows prominent absorptions at 2112 (s), 928, 882, 798 (vs), 784 (vs), 674, and 452 cm-1. The mass spectrum confirms the presence of the molecular ion at m/e 156-172 [H Ge20]+. 

A digermoxane compound, (GeH3)20 with the Ge-O-Ge angle of 126.5°, can be prepared by hydrolysis of GeHsCl or from the reaction of (H3Ge)2S with HgO. Compared to the predicted value of 182.7 pm, the shorter distance of Ge O, 176.6pm, is attributed to some degree of p-d 7T bonding. 

Ge(C6H5)sNa Sodium, (triphenyl-germyl)-, 6 72, 74 [Ge(C6H6)3laO Digermoxane, hexa-phenyl-, 6 78... 

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