Multiple cluster CH activations and transformations of furan by triosmium carbonyl complexes

Reaction of Os3(CO)10(NCMe)2 with the triosmium furyne complex Os3(CO)9(μ3,η2-C4H2O)(μ-H)2, 1 yielded the bis-triosmium complex 2 containing a bridging furyenyl ligand by CH activation at the uncoordinated C-C double bond. Heating 2 led to additional CH activation with formation of the first furdiyne C4O ligand in the complex Os3(CO)9(μ-H)2(μ3-η2-2,3-μ3-η2-4,5-C4O)Os3(CO)9(μ-H)2, 3. The furdiyne ligand in 3 was subsequently ring-opened and decarbonylated to yield products 4 and 5 containing novel bridging C3 ligands. Complex 2 also undergoes ring opening to yield an intermediate Os3(CO)9(μ-H)(μ3-η2-μ-η2-CH-C-CH-C[double bond, length as m-dash]O)Os3(CO)10(μ-H), 6 which was also decarbonylated thermally to yield 4 and 5. All products were characterized by a combination of IR, NMR, mass spec and single-crystal X-ray diffraction analyses.