Separation of Metal Binding and Electron Transfer Sites as a Strategy To Stabilize the Ligand-Reduced and Metal-Oxidized Form of [Mo(CO)4L]

Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F11%3A00369241" target="_blank" >RIV/61388955:_____/11:00369241 - isvavai.cz</a>
Result on the web
<a href="http://dx.doi.org/10.1021/om2007858" target="_blank" >http://dx.doi.org/10.1021/om2007858</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/om2007858" target="_blank" >10.1021/om2007858</a>

Result language
angličtina
Original language name
Separation of Metal Binding and Electron Transfer Sites as a Strategy To Stabilize the Ligand-Reduced and Metal-Oxidized Form of [Mo(CO)4L]
Original language description
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 aseven-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 toa 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.
Czech name
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Czech description
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Type
J<sub>x</sub> - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)
CEP classification
CF - Physical chemistry and theoretical chemistry
OECD FORD branch
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Project
<a href="/en/project/GA203%2F09%2F0705" target="_blank" >GA203/09/0705: Transfer of charge in single and assembled molecules</a><br>
Continuities
Z - Vyzkumny zamer (s odkazem do CEZ)

Publication year
2011
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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