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Reactions involving hydrogen transfer from triosmium clusters to an activated nitrile

1981; Elsevier BV; Volume: 219; Issue: 1 Linguagem: Inglês

10.1016/0022-328x(81)85013-9

1872-8561

Richard D. Adams, Dean A. Katahira, Li‐Wu Yang,

Organometallic Complex Synthesis and Catalysis

The reactions of H2Os3(CO)10, Ia and H2Os3(CO)9PMe2Ph, Ib with CF3CN have been investigated. Both la and Ib react with CF3CN to give the products HOs3[μ-η2-(CF3)CNH](CO)9Land HOs3[μ-η1-NC(H)CF3](CO)9L, IIa, IIIa, L = CO; IIb and IIIb, L = PMe2Ph. IIb and IIIb have been characterized crystallographically. In each, one nitrile molecule was added to the cluster and one hydride ligand was transferred to the nitrile ligand, but in IIb the hydride was transferred to the nitrogen atom to form a CF3CNH ligand which bridges an edge of the cluster while in IIIb the hydride was transferred to the carbon atom to form a CF3(H)CN ligand which also bridges an edge of the cluster. On the basis of spectroscopic measurements IIa and IIIa are believed to have analogous structures. An isotope scrambling experiment established that the formation of Ilia occurs by an intramolecular process. IIa was decarbonylated to yield the compound HOs3[μ3-η2-(CF3)CNH](CO)9, which is believed to contain a triply-bridging iminyl ligand. Ilia reacts with PMe2Ph to give two mono-substitution products, one of which is IIIb.