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Z. Naturforsch. 2012,
67b, 532 – 542
doi:10.5560/ZNB.2012-0144
Reactivity of 4-Nitrosoanilines Towards Dimeric Halogenido-bridged Complexes of Iridium(III) and Rhodium(III) of the Type [(η5-C5Me5)MX2]2
Department of Chemistry, Ludwig-Maximilian-University Munich, Butenandtstraße 5-13 (House D), D-81377 Munich, Germany
Reprint requests to Prof. Dr. I.-P. Lorenz. E-mail:
ipl@cup.uni-muenchen.de
Received May 25, 2012 / published online July 6, 2012
Dedicated to Professor Wolfgang Beck on the occasion of his 80th birthday
The synthesis, spectroscopic characterization and crystal structures of new C-nitrosoaryl complexes of iridium(III) and rhodium(III) are reported. The reactions of the μ2-halogenido-bridged dimers [(η5-C5Me5)IrX2]2 [X = Cl (1a), Br (1b), I (1c)] and [(η5-C5Me5)RhCl2]2 (2a) with N,N-dimethyl- (3) and N,N-diethyl-4-nitrosoaniline (4) yield the mononuclear complexes [(η5-C5Me5)MX2(3)] [M = Ir, X = Cl
(5a), Br (5b), I (5c); M = Rh, X = Cl (7a)] and [(η5-C5Me5)MX2(4)] [M = Ir, X = Cl (6a), Br (6b), I (6c); M = Rh, X = Cl (8a)]. All new compounds were characterized by their melting points, NMR, IR and mass spectra as well as in selected cases by UV/Vis spectroscopy. The X-ray structure analyses revealed a slightly distorted pseudo-octahedral configuration (“three-legged pianostool”) and σ-N coordination of the C-nitroso ligand.
Key words: C-Nitroso Anilines, N Ligand, Iridium, Rhodium