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Ligand-Centred Reactivity of Bis(picolyl)amine Iridium: Sequential Deprotonation, Oxidation and Oxygenation of a "Non-Innocent" Ligand
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SYSNO ASEP 0336077 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Ligand-Centred Reactivity of Bis(picolyl)amine Iridium: Sequential Deprotonation, Oxidation and Oxygenation of a "Non-Innocent" Ligand Title Reaktivita lokalizovaná na ligandu v bis(picolyl)aminových komplexech iridia; Sekvenční deprotonace, oxidace a oxygenace ‘Non-Innocent’ ligandu Author(s) Tejel, C. (ES)
del Río, M. P. (ES)
Ciriano, M. A. (ES)
Reijerse, E. J. (DE)
Hartl, F. (GB)
Záliš, Stanislav (UFCH-W) RID, ORCID
Hetterscheid, D. G. H. (NL)
Tsichlis i Spithas, N. (NL)
de Bruin, B. (NL)Source Title Chemistry - A European Journal. - : Wiley - ISSN 0947-6539
Roč. 15, č. 44 (2009), s. 11878-11889Number of pages 12 s. Language eng - English Country DE - Germany Keywords bis(picolyl)amine ; iridium ; ligand radical ; oxygenation Subject RIV CG - Electrochemistry R&D Projects OC 139 GA MŠMT - Ministry of Education, Youth and Sports (MEYS) KAN100400702 GA AV ČR - Academy of Sciences of the Czech Republic (AV ČR) CEZ AV0Z40400503 - UFCH-W (2005-2011) UT WOS 000272109100013 DOI 10.1002/chem.200901017 Annotation 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 [M-I(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 O-2 gave the neutral carboxamido complex [Ir(cod)(py-CH2-N-CO-py)] via the ligand radical complex [3]* as a detectable intermediate. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2010
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