Abstract
Treatment of OsCl2(PPh3)3 with HC≡CAr (Ar = Ph, p-tolyl) produced the η3-allenylcarbene complexes OsCl2(═CAr-η2-CH═C═CHAr)(PPh3)2. Reactions of the η3-allenylcarbene complexes with gold alkynyls Au(C≡CR)(PPh3) (R = Ph, p-tolyl, TMS, nBu, CH(OEt)2) or copper(I) alkynyls Cu(C≡CR) (R = Ph, TMS) in the presence of HNEt3Cl produced the osmabenzynes Os{≡CC(R)═C(CH2Ar)CH═CAr}Cl2(PPh3)2. Computational studies suggest that the osmabenzynes are formed through electrocyclization of osmium alkynyl-allenylcarbene intermediates followed by protonation with HNEt3Cl.
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