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An iridium-mediated C–H activation/CO2-carboxylation reaction of 1,1-bisdiphenylphosphinomethane

AuthorsLanger, J.; Fabra-Caro, María J.; García-Orduña, P. ; Lahoz, Fernando J. ; Görls, H.; Oro, Luis A. ; Westerhausen, M.
Issue Date2010
PublisherRoyal Society of Chemistry (Great Britain)
CitationDalton Transactions 39(33): 7813-7821 (2010)
AbstractThe reaction of 1,1-bisdiphenylphosphinomethane (dppm, 4 eq.) with [IrCl(coe)2]2 results in a solvent dependent equilibrium from which the complexes [IrCl(dppm)(dppm-H)(H)] (1) and [Ir(dppm) 2]Cl (2) were isolated. When 2 is dissolved in methanol, [IrCl(dppm)2(H)][OCH3] (4) is formed as dominant species in solution. The C-H activation reaction which leads to 1 and 4 can be suppressed by adding an additional dppm ligand per iridium center resulting in the formation of [Ir(dppm)3]Cl (5). If the reaction of dppm with [IrX(coe)2]2 (X = Cl, I) is performed under an atmosphere of CO2 the complexes [IrX(dppm)(H){(Ph2P) 2C-COOH}] (6: X = Cl; 7: X = I) are formed by a CH activation/CO 2 carboxylation sequence. The reaction of 6 with NH4PF yields [IrCl(dppm)2(H)]PF6.(10). Additionally the lithium compounds [Li(dme)2(dppm-H)] (3) and [Li(dme){(Ph2P) 2CHCOO}]2 (8) were prepared for comparison. The molecular structures of the compounds 1, 3, 5, 7, 8 and of the related iridium complex [IrCl(dppm)2(H)]I (11) are reported. © The Royal Society of Chemistry 2010.
Identifiersdoi: 10.1039/C0DT00230E
issn: 1477-9226
e-issn: 1477-9234
Appears in Collections:(ICMA) Artículos
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