AbstractThe use of a new electron‐withdrawing germane, H2Ge[3,5‐(CF3)2C6H3]2 (3), has facilitated the isolation and characterization of three new complexes implicated in the dehydrogenative coupling of bisarylgermanes by Pt0‐phos‐phane complexes. The intermediates include a digermyl species, trans‐[(Et3P)2Pt{GeH(Ar)2}2] (7), a bound digermane showing the first stage of Ge‐Ge catenation, cis‐[(Et3P)2Pt(H){Ge(Ar)2‐GeH(Ar)2}] (8), and the Ge‐H activated form of this product, [(Et3P)2HPtGe(Ar)2‐Ge(Ar)2PtH(PEt3)2] (6). Complexes such as 6 and 8 have not previously been isolated as intermediates in dehydrogenative coupling reactions. An X‐ray crystal structure was determined for complex 6, confirming the cis geometry of the hydrogen and germanium ligands; this provides yet another example of the stability of germyl hydrides towards reductive elimination. A similar cis geometry was observed for complex 8. Performing the dehydrogenative coupling reaction under a CO2 atmosphere failed to yield any products containing trapped germylene species.