Synthesis, characterization, and X-ray structures of three iridium(III)-hydrido-cyclometallated-imine complexes, including the first reported hydrido-(η1-imine)-Ir complex

Lorenzini, Fabio; Marcazzan, Paolo; Patrick, Brian O.; James, Brian R.
March 2008
Canadian Journal of Chemistry;Mar2008, Vol. 86 Issue 3, p253
Academic Journal
Reactions of cis,trans,cis-[Ir(H)2(PPh3)2(solv)2]PF6 (solv = MeOH or Me2CO) with the imines HN=CPh2, (o-HOC6H4)C(Me)=NCH2Ph, and PhC(H)=N(p-F-C6H4) in MeOH or acetone under Ar give the complexes [IrH{NH=C(Ph)(o-C6H4)}(NH=CPh2)(PPh3)2]PF6 (3), [IrH{PhCH2N=C(Me)(o-C6H3OH)}(solv)(PPh3)2]PF6, where solv = MeOH (4) or Me2CO (4a), and [IrH{N(p-F-C6H4)=CH(o-C6H4)}(Me2CO)(PPh3)2]PF6 (5a), which have been isolated and characterized. The imine (C6F5)C(H)=NPh is unreactive toward the Ir precursors. The X-ray structures of 3, 4·2MeOH, and 5a·1/2Me2CO show an η2-N,C-imine moiety coordinated via the N atom and an orthometallated-C atom. Complex 3, which contains both an orthometallated imine and an η1-imine, is the first structurally characterized hydrido-(η1-imine)-Ir complex. Comparisons are made with data for the corresponding Rh systems.Key words: iridium, hydride complexes, imines, fluoroimines, phosphine complexes, orthometallation, crystallography, NMR spectroscopy. Les réactions du cis,trans,cis-[Ir(H)2(PPh3)(solv)2]PF6 (solv = MeOH ou Me2CO) avec les imines HN=CPh2, (o-HOC6H4)C(Me)=NCH2Ph et PhC(H)=N(p-F-C6H4), en solution dans le MeOH ou l’acétone, sous une atmosphère d’argon, conduit à la formation des complexes [IrH{NH=C(Ph)(o-C6H4)}(NH=CPh2)(PPh3)2]PF6 (3), [IrH{PhCH2N=C(Me)(o-C6H3OH)}(solv)(PPh3)2]PF6 dans lequel solv = MeOH (4) ou Me2CO (4a) et [IrH{N(p-F-C6H4)=CH(o-C6H4)}(Me2CO)(PPh3)2]PF6 (5a) qui ont été isolés et caractérisés. L’imine (C6F5)CH=NPh n’est pas réactive vis-à-vis les précurseurs Ir. Les structures des composés 3, 4·2MeOH et 5a·1/2Me2CO telles que déterminées par diffraction des rayons X ont permis de montrer la présence d’une portion η2-N,C-imine coordinée par le biais de l’atome d’azote et d’un atome de carbone orthométallé. Le complexe 3 qui comporte une imine orthométallée ainsi qu’une η1-imine est le premier complexe hydrido-(η1-imine)-Ir à être caractérisée d’un point de vue structural. On a effectué des comparaisons avec des données pour les systèmes correspondants du rhodium.Mots-clés : iridium, complexes d’hydrure, imines, fluoroimines, complexes de phosphine, organométallation, cristallographie, spectroscopie RMN.[Traduit par la Rédaction]


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