899809-36-0Relevant academic research and scientific papers
Preparation of five- and six-coordinate aryl(hydrido) iridium(III) complexes from benzene and functionalized arenes by C-H activation
Werner, Helmut,Hoehn, Arthur,Dziallas, Michael,Dirnberger, Thomas
, p. 2597 - 2606 (2007/10/03)
The reaction of the in situ generated cyclooctene iridium(i) derivative trans-[IrCl(C8H14)(PiPr3)2] with benzene at 80 °C gave a mixture of the five-coordinate dihydrido and hydrido(phenyl) iridium(iii) complexes [IrH2(Cl)(PiPr 3)2] 2 and [IrH(C6H5)(Cl)(PiPr 3)2] 3 in the ratio of about 1: 2. The chloro- and fluoro-substituted arenes C6H5X (X = Cl, F), C 6H4F2 and C6H4F(CH 3) reacted also by C-H activation to afford the corresponding aryl(hydrido) iridium(iii) derivatives [IrH(C6H4X)(Cl) (PiPr3)2] 7, 8, [IrH(C6H3F 2)(Cl)(PiPr3)2] 9-11 and [IrH{C 6H3F(CH3)}(Cl)(PiPr3)2] 12, 13, respectively. The formation of isomeric mixtures had been detected by 1H, 13C, 19F and 31P NMR spectroscopy. Treatment of 3 and 7-13 with CO gave the octahedral carbonyl iridium(iii) complexes [IrH(C6H3XX′)(Cl)(CO) (PiPr3)2] 5, 14-20 without the elimination of the arene. The reactions of trans-[IrCl(C8H14)(PiPr3) 2] with aryl ketones C6H5C(O)R (R = Me, Ph), aryl ketoximes C6H5C(NOH)R (R = Me, Ph) and benzaloxime C6H5C(NOH)H resulted in the formation of six-coordinate aryl(hydrido) iridium(iii) compounds 21-25 with the aryl ligand coordinated in a bidentate κ2-C,O or κ2-C,N fashion. With C6H5C(O)NH2 as the substrate, the two isomers [IrH{κ2-N,O-NHC(O)C6H5}(Cl)(PiPr 3)2] 26 and [IrH{κ2-C,O-C 6H4C(O)NH2}(Cl)(PiPr3)2] 27 were prepared stepwise. Treatment of trans-[IrCl(C8H 14)(PiPr3)2] with benzoic acid gave the benzoato(hydrido) complex [IrH{κ2-O,O-O2CC 6H5}(Cl)(PiPr3)2] 29 which did not rearrange to the κ2-C,O isomer. The Royal Society of Chemistry 2006.
