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Separation of Metal Binding and Electron Transfer Sites as a Strategy To Stabilize the Ligand-Reduced and Metal-Oxidized Form of [Mo(CO)4L]
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SYSNO ASEP 0369241 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Separation of Metal Binding and Electron Transfer Sites as a Strategy To Stabilize the Ligand-Reduced and Metal-Oxidized Form of [Mo(CO)4L] Author(s) Bulak, E. (DE)
Varnali, T. (TR)
Schwederski, B. (DE)
Bubrin, D. (DE)
Fiedler, Jan (UFCH-W) RID, ORCID
Kaim, W. (DE)Source Title Organometallics. - : American Chemical Society - ISSN 0276-7333
Roč. 30, č. 23 (2011), s. 6441-6445Number of pages 5 s. Language eng - English Country US - United States Keywords Electron Transfer Sites ; [Mo(CO)4L] ; metal carbonyl complexes Subject RIV CF - Physical ; Theoretical Chemistry R&D Projects GA203/09/0705 GA ČR - Czech Science Foundation (CSF) CEZ AV0Z40400503 - UFCH-W (2005-2011) UT WOS 000297537500014 DOI 10.1021/om2007858 Annotation The zerovalent metal in [Mo(CO)4(bmiq)] binds the two imidazole-N-imine donors of 2,3-bis(1-methylimidazol-2-yl)quinoxaline (bmiq), resulting in a seven-membered chelate ring coordinated in cis configuration. DFT calculations confirm the preference for a seven-membered vs five-membered ring chelation alternative as well as the experimental structural parameters. The complex is reversibly reduced in CH2Cl2 at −2.08 V and reversibly oxidized at −0.14 V vs ferrocenium/ferrrocene. The facilitated oxidation to a stable cation is attributed to the donor effect from the imidazole rings. In agreement with the DFT-calculated characteristics of the HOMO and LUMO, the in situ EPR studies at a Pt electrode reveal a MoI signature for the cation (g1 = 1.967, g2 = 1.944, g3 = 1.906; Aiso(95,97 Mo) = 50 G) and a quinoxaline radical-type EPR spectrum with dominant 14N coupling (2 N) of 6.0 G for the anion. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2012
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