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- W1996787420 abstract "An IrI complex of an acetamidinato ligand was synthesized by reaction of N,N′-diphenylacetamidine, PhNC(Me)NHPh, with either MeLi and [{Ir(cod)}2(μ-Cl)2] or [{Ir(cod)}2(μ-OMe)2] and was characterized by X-ray crystallography as a mononuclear complex, [Ir{PhNC(Me)NPh}(cod)] (1; where cod = 1,5-cyclooctadiene). Reaction of 1 with CO afforded a dinuclear carbonyl complex, [{Ir(CO)2}2{μ-PhNC(Me)NPh-κN:κN′}2] (2), as indicated by EI mass spectrometry and solution- and solid-state IR spectroscopy [νCO (n-pentane) = 2067, 2034 and 1992 cm−1]. Activation of O2 by 1 in solution at 20 °C was irreversible and produced an (alkene)peroxoiridium(III) intermediate, [Ir{PhNC(Me)NPh}(cod)(O2)] (3), which was characterized by one- and two-dimensional NMR techniques and IR spectroscopy (for 3, νOO = 860 cm−1; for 3–18O2, νOO = 807 cm−1). Complex 3 oxidized PPh3 to OPPh3, and its decay in the absence of added substrates followed by reaction with cod yielded 4-cycloocten-1-one and a minor amount of 1. In comparison with the results for the previously reported guanidinato complex [Ir{PhNC(NMe2)NPh}(cod)(O2)] (4), the formation of 3 and its reaction with PPh3 are significantly faster, indicating considerable ligand effects in these reactions." @default.
- W1996787420 created "2016-06-24" @default.
- W1996787420 creator A5025861594 @default.
- W1996787420 creator A5033344535 @default.
- W1996787420 date "2014-01-01" @default.
- W1996787420 modified "2023-10-18" @default.
- W1996787420 title "Formation and reactivity of an (alkene)peroxoiridium(<scp>iii</scp>) intermediate supported by an amidinato ligand" @default.
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- W1996787420 doi "https://doi.org/10.1039/c3dt52283k" @default.
- W1996787420 hasPubMedId "https://pubmed.ncbi.nlm.nih.gov/24121680" @default.
- W1996787420 hasPublicationYear "2014" @default.
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