Ligand‐Centred Reactivity of Bis(picolyl)amine Iridium: Sequential Deprotonation,Oxidation and Oxygenation of a “Non‐Innocent” Ligand |
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| Authors: | Cristina Tejel Dr M Pilar del Río Dr Miguel A Ciriano Prof Dr Eduard J Reijerse Dr František Hartl Prof Stanislav Záliš Dr Dennis G H Hetterscheid Dr Nearchos Tsichlis i Spithas Bas de Bruin Dr |
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| Institution: | 1. Instituto de Ciencia de materiales de Aragón (ICMA), CSIC‐Universidad de Zaragoza, Pedro Cerbuna 12, 50007 Zaragoza (Spain), Fax: (+34)?976‐791187;2. Max‐Planck Institute for Bio‐Inorganic Chemistry, Stiftstrasse 34–36, 45470 Mülheim an der Ruhr (Germany);3. University of Reading, Department of Chemistry, Whiteknights, PO Box 224, Reading RG6 6AD Berkshire (UK);4. J. Heyrovsky Institute of Physical Chemistry, Academy of Sciences of the Czech Republic, Dolej?kova 3, 182 23 Prague 8 (Czech Republic);5. Van ‘t Hoff Institute for Molecular Sciences (HIMS), University of Amsterdam (UvA), Nieuwe Achtergracht 166, 1018 WV Amsterdam (The Netherlands), Fax: (+31)?20‐525‐5604 |
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| Abstract: | Treatment of Ir(bpa)(cod)]+ complex 1 ]+ with a strong base (e.g., tBuO?) led to unexpected double deprotonation to form the anionic Ir(bpa?2H)(cod)]? species 3 ]?, via the mono‐deprotonated neutral amido complex Ir(bpa?H)(cod)] as an isolable intermediate. A certain degree of aromaticity of the obtained metal–chelate ring may explain the favourable double deprotonation. The rhodium analogue 4 ]? was prepared in situ. The new species M(bpa?2H)(cod)]? (M=Rh, Ir) are best described as two‐electron reduced analogues of the cationic imine complexes MI(cod)(Py‐CH2‐N?CH‐Py)]+. One‐electron oxidation of 3 ]? and 4 ]? produced the ligand radical complexes 3 ]. and 4 ].. Oxygenation of 3 ]? with O2 gave the neutral carboxamido complex Ir(cod)(py‐CH2‐N‐CO‐py)] via the ligand radical complex 3 ]. as a detectable intermediate. |
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| Keywords: | bis(picolyl)amine iridium ligand radical non‐innocent ligands oxygenation |
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