N–N Double-Bond Cleavage and Azobenzene Rearrangement with C–C Bond Formation Induced by a Germylene

Abstract

The diarylgermylene Ge(ArMe6)2 (ArMe6 = C6H3-2,6-(C6H2-2,4,6-Me3)2) was shown to react with azobenzene at room temperature to yield the Ge(IV) diamido products (ArMe6)2Ge{N(H)(Ph)-o(Ph)(H)N} (1a) and (ArMe6)2Ge{N(H)-o-C6H4N(Ph)} (1b), which were characterized via 1H and 13C NMR spectroscopy and by X-ray crystallography. Treatment of Ge(ArMe6)2 with a bulkier diazene, 1,2-bis(2,6-diethylphenyl)diazene or 1,2-bis(1,3,5-trimethylphenyl)diazene, even at elevated temperature did not afford N–N bond cleavage, and only C–H activation of the germylene was observed. Treatment of the analogous tin species Sn(ArMe6)2 under the same conditions afforded no reaction.