- Directing iridium-catalyzed C-C bond formation by selection of the ancillary ligands: Polymerization and cyclotrimerization of alkynes
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The ability of organoiridium derivatives of catalyzing oligomerization and polymerization of terminal alkynes is markedly influenced by the nature of non-participative ligands coordinated to the metal. The dimeric species [Ir(cod)Cl]2 and [Ir(c
- Farnetti, Erica,Filipuzzi, Serena
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p. 467 - 473
(2010/04/28)
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- Iridium-catalyzed formation of trans-polyphenylacetylene by alkyne polymerization
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The iridium(I) compounds HIr(cod)(PR3)2 (cod: 1,5-cyclooctadiene; PR3: Ph3, P(p-MeOC6H 4)3, P(o-MeOC6H4)Ph2, PCyPh2, PCy2Ph
- Marigo, Mauro,Millos, Dunja,Marsich, Nazario,Farnetti, Erica
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p. 319 - 329
(2008/10/08)
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- Synthesis and reactivity of alkoxy(η4-cycloocta-1,5-diene)iridium(I) and -rhodium(I) M(OR)(cod)(PCy3) Compounds. X-ray crystal structure of the alkynyl Ir(C≡CPh)(cod)(PCy3) complex
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The synthesis and reactivity of the alkoxy(η4-cycloocta-1,5-diene)iridium(I) Ir(OR)(cod)(PCy3) (R = Me, Et, or Ph; Cy = cyclohexyl; cod = cycloocta-1,5-diene) complexes are described. They are prepared by reaction of [Ir(μ-OR)(cod)]2 with PCy3. The synthesis of Rh(OPh)(cod)(PCy3) by reaction of [Rh(μ-OMe)(cod)]2 with PCy3 and PhOH is also reported. Treatment of [Ir(μ-OMe)(cod)]2 with PCy3 in methanol for 24 h gives a mixture of the hydrido IrH5(PCy3)2 and mer-IrH3(CO)(PCy3)2 complexes. Ir(OEt)(cod)(PCy3) reacts with HSiR3 (SiR3 = SiEt3 or SiMe2Ph) leading to the formation of IrH2(SiR3)(cod)(PCy3). Ir(OR)(COd)(PCy3) undergoes alkoxy exchange with phenol. Alkoxy exchange is also observed in the reaction of Ir(OEt)(COd)(PCy3) with phenylacetylene (HC≡CPh); the resulting Ir(C≡CPh)(cod)(PCy3) complex has been characterized by X-ray diffraction. Ir(C≡CPh)(cod)(PCy3): triclinic, space group P1, Z = 2, a = 12.3726 (6) A?, b = 11.1529 (4) A?, c = 12.4738 (5) A?, α = 105.307 (4)°, β = 101.845 (3)°, and γ = 107.607 (4)°. The structure was solved by Patterson and difference direct methods and refined to a conventional agreement factor of 0.034. The coordination around iridium is slightly distorted square planar, with a Ir-C(1) distance of 1.998 (6) A? and a C(1)-C(2) (C≡C) bond length and C(1)-C(2)-C(3) angle of 1.200 (10) A? and 176.5 (8)°, respectively.
- Fernández, María J.,Esteruelas, Miguel A.,Covarrubias, Macarena,Oro, Luis A.,Apreda, María-Carmen,Foces-Foces, Concepción,Cano, Felix H.
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p. 1158 - 1162
(2008/10/08)
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