The use of metal hydrides such as NaBH4 as hydrogen-storage materials has recently received substantial research attention on account of the worldwide demand for the development of efficient hydrogen-production, -storage, and -transportation systems. Here, we report the quantitative production of H2 gas from a germanium hydride, Ph2GeH2, mediated by an iron catalyst at room temperature via dehydrogenative coupling, concomitant with the formation of (GePh2)5. Of particular importance is that Ph2GeH2 can be facilely recovered from (GePh2)5 by contact with 1 atm of H2 or PhICl2/LiAlH4 at 0 °C or 40 °C, respectively. A detailed reaction mechanism for the iron-catalyzed dehydrogenative coupling of Ph2GeH2 is proposed based on the isolation of four intermediate iron species.
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