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Type: Artigo de periódico
Title: Kinetics Of Conversion Of [ir4(co)11(pph2aupph3)] Into [ir4(co)10(μ-pph2)(μ-aupph3)] And Their Structural Characterization
Author: Livotto F.S.
Vargas M.D.
Braga D.
Grepioni F.
Abstract: Deprotonation of [Ir4(CO)11(PPh2H)] 1 in the pressence of [Au(PPh3)]PF6 yields the novel species [Ir4(CO)11(PPh2AuPPh3)] 2 which possesses a tetrahedral framework bearing a terminally bonded PPh2AuPPh3 ligand. Changing the order of addition of the reagents results in the formation of [Ir4(CO)10(μ-PPh2)(μ-AuPPh3)] 4 with bridging phosphido and Au(PPh3)+ units. Reaction of 4 with PPh3 yields [Ir4(CO)9(PPh3)(μ-PPh 2)(μ-AuPPh3)] 6, while with the more basic phosphine P(C6H4OMe-4)3 substitution of the PPh3 at the Au(PPh3)+ unit occurs producing [Ir4(CO)10(μ-PPh2){μ-AuP(C 6H4PMe-4)3}]. Deprotonation of [Ir4(CO)10(PPh3)(PPh2H)] in the presence of [Au(PPh3)]PF6 yields [Ir4(CO)10(PPh3)(PPh2AuPPh 3)], which undergoes rearrangement to 6. The kinetics of decarbonylation of compound 2 and give 4 has been investigated and a dissociative mechanism is suggested, confirmed by the activation parameters ΔH‡ = 135.6 ± 3.8 kJ mol-1 and ΔS‡ = 81.2 ± 10.9 J K-1 mol-1.
Rights: fechado
Identifier DOI: 10.1039/DT9920000577
Date Issue: 1992
Appears in Collections:Unicamp - Artigos e Outros Documentos

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