93240-02-9Relevant academic research and scientific papers
Vinyliden-Uebergangsmetallkomplexe VIII. Die stufenweise Umwandlung von Alkiniridium(I)- in Alkinyl(hydrido)iridium(III)- und Vinylideniridium(I)-Komplexe
Hoehn, A.,Werner, H.
, p. 255 - 272 (2007/10/02)
Square-planar vinylidene iridium(I) complexes trans-i3)2> (XIa-c) have been prepared in two steps from trans-i3)2> (VIIIa-c) via the isolated (for R=Me, Ph) alkynyl(hydrido) iridium(III) isomers i3)2> (IXb, c).The reaction of 2 and PPri3 with HCCSiPh3 leads directly to the formation of i3)2> (IXe).The vinylidene complexes XIa-c react with HBF4 to give first i3)2>+ (XIIa-c) and then by intramolecular rearrangement to give the BF4 salts of the carbyne iridium cations trans-+ (XIIIa-c).In solution, an equilibrium exists between XIIIa-c and XIIa-c which lies almost exclusively towards XIIIa-c.Treatment of XIIIa-c with NaH in benzene regenerates the vinylidene iridium compounds XIa-c.The hydroxo, iodo and methyl derivatives, trans-i3)2> (X= OH: XVa-c; X= I: XVIa-c; X= CH3: XVIIa, c), are prepared from XIa-c by ligand displacement using KOH, NaI and LiCH3 as reagents. trans-i3)2> (XVIa) reacts with CO to give the octahedral alkynyl(hydrido)iridium(III) complex i3)2(CO)> (XVIII).From XIc and XIa as starting materials, the vinyl iridium(III) compounds i3)2(CO)> (XIX) and i3)2> (XX) have also been obtained.
SYNTHESE UND REAKTIVITAET DES DIPHENYLACETYLENIRIDIUM KOMPLEXES C5H5Ir(C2Ph2)PPri3 UND BILDUNG EINER ISOMEREN IRIDAINDEN-VERBINDUNG
Werner, H.,Hoehn, A.
, p. 105 - 114 (2007/10/02)
trans-i)2> complexes are prepared from 2, PPr3i and C2R2 (R = H, Me, Ph) via the intermediate i)2>.With phenylacetylene, a mixture of two isomers, trans-i)2> and IrHCl(C2Ph)(PPr3i)2 is formed which reacts with pyridine to give IrHCl(C2Ph)(py)(PPr3i)2.Reaction of trans-i)2> with NaC5H5 yields the compound C5H5Ir(C2Ph2)PPr3i (VI) which is transformed via the vinyl complex C5H5Ir(CPh=CHPh)(OCOCF3)PPr3i (VII) into the iridaindene derivative IX.Using VII as the starting material, C5H5Ir(OCOCF3)2PPr3i, C5H5Ir(CPh=CHPh)(I)PPr3i and C5H5Ir(CPh=CHPh)(CH3)PPr3i are also obtained.Treatment of VI with Br2 and I2 respectively yields the complexes C5H5IrX2(PPr3i) (XII, X = Br; XIII, X = I), of which XIII reacts with CH3MgI to give C5H5Ir(CH3)2PPr3i.
