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Type: Artigo de periódico
Title: Synthesis And Structural Characterization Of [ir4(μ-co)(co)7{μ4-η3-ph 2pc(h)c(ph)pcbut}(μ-pph2)]: Alkyne-phosphaalkyne Coupling And Formation Of A Novel 2-phosphabutadienylphosphine Ligand
Author: Araujo M.H.
Hitchcock P.B.
Nixon J.F.
Vargas M.D.
Abstract: Reaction of [Ir4(μ-H)(CO)9(Ph2PC=CPh)(μ-PPh 2)]1 with PsCBut in CH2Cl2, at 35°C, for 4 h yields the novel compound [Ir4(μ-CO)(CO)7{μ4-η3-Ph 2PC(H)C(Ph)PCBut}(μ-PPh2)] 2, which contains the 2-phosphabutadienylphosphine chain. Compound 2 is also formed upon thermolysis of [Ir4(CO)10(Ph2PC=CPh)(PPh2H)] 3 in the presence of P=CBut in thf, at 40°C, for 48 h. Small amounts of [Ir4(μ-CO)(CO)7(μ3-η 2-HCCPh)(μ-PPh2)2] 4 are always obtained from both reactions, because of the competing rates of the transformations of 1 and 3 into 4 and of their reactions with P≡CBut. Compound 2 was characterized by analytical and spectroscopic studies such as FAB ms, 1H, 31P, 13C, 2D 31P-1H HETCOR, nOe difference and DEPT NMR experiments, which led to its formulation and established the coupling between the coordinated Ph2PC≡CPh and P≡CBut and the migration of the hydride to the Cα of the Ph2PC≡CPh ligand. However, it was impossible to establish unambiguously if cleavage of the P-Cspbond of the Ph2PC≡CPh ligand had occurred and the mode of interaction of the organophosphorus chain. An X-ray diffraction study of compound 2 established a butterfly arrangement of iridium atoms with the new ligand interacting with the metal framework via four σ bonds and the PPh2 phosphorus lone pair.
Rights: aberto
Identifier DOI: 
Date Issue: 1998
Appears in Collections:Unicamp - Artigos e Outros Documentos

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