A series of phosphorus-substituted germanium(II) complexes, L1GeR [L1 = CH{(CMe)(2,6-iPr2C6H3N)}2; 2, R = PPh2; 4, R = OPPh2; 5a, R = OP(O)Ph2; 5b, R = OP(O) (OnBu)2; 6a, R = OP(S)Ph2; 6b, R = OP(S)(OEt)2], were synthesized through the direct activation of various organic phosphorus compounds by N-heterocyclic ylide-like germylene 1.

We report herein the first example of the conversion of metallabenzyne II and isometallabenzene III. The osmium hydride vinylidene complex 1 reacts with HCCCH(OEt)2 to give osmabenzyne 3 via isoosmabenzene 2. Compound 3 exhibits high thermal stability in air. Nonetheless, nucleophilic attack at 3 provides isoosmabenzenes 4 a and 4 b, or opens the ring to produce 5 a and 5 b.