The activation of dydrogen (H2) (either homolytically or heterolytically) has been extensively examined by both experimentalists and theoreticians, as this process has versatile applications to synthesis, catalysis and energy storage.[1] Previously, transition metal based complexes were widely applied as catalysts to activate H2. However, since 2005, main group element based complexes have emerged which can activate H2 and other small molecules under mild conditions, e.g. carbenes,[2] a stable digermyne,[3] distannynes,[4] and �Frustrated Lewis Pairs� (FLP).[5] Such advances highlight the potential for main group systems to replace expensive, toxic transition metal compounds in many processes reliant on E-H bond activations. We will present recent results concerned with the synthesis of the first amido digermyne, LGeGeL (dGe-Ge=2.7 �) which displays remarkable reactivity towards H2 (Figure 1). Our findings indicate the H2 activation can be realized at unprecedentedly low temperatures (ca. -10�C) either in solution or the solid state to yield a mixed-valent GeIII-GeI hydride complex, LGeGe(H)2L. A computational analysis of the mechanism of this reaction will be presented, as will preliminary results on the reactivity of LGeGeL towards NH3, CO2 and other small molecules.Figure 1 reaction of digermyne with H2 and reaction of LGeCl with Li[HB(sBu)3] References:[1]            K. Gregory J, Journal of Organometallic Chemistry 2009 , 694, 2648-2653.[2]            (a) A. L. Kenward, W. E. Piers, Angewandte Chemie International Edition 2008 , 47, 38-41; (b) D. Bourissou, O. Guerret, F. P. Gabba�, G. Bertrand, Chemical Reviews 1999 , 100, 39-92.[3]            G. H. Spikes, J. C. Fettinger, P. P. Power, Journal of the American Chemical Society 2005 , 127, 12232-12233.[4]            Y. Peng, M. Brynda, B. D. Ellis, J. C. Fettinger, E. Rivard, P. P. Power, Chemical Communications 2008 , 6042-6044[5]            (a) D. W. Stephan, G. Erker, Angewandte Chemie International Edition 2010 , 49, 46-76; (b) G. C. Welch, R. R. S. Juan, J. D. Masuda, D. W. Stephan, Science 2006 , 314, 1124-1126.

Activation of E-H bonds (E = H, N etc.) by a digermyne with a Ge-Ge single bond

244th National Meeting (2012)

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