Redox Site Confinement in Highly Unsymmetric Dimanganese Complexes

Cite This

Files in this item

Checksum: MD5:b113ef53451a2b6271ee462d853bf309

SHENG, Tianlu, Sebastian DECHERT, Isabella HYLA-KRYSPIN, Rainer WINTER, Franc MEYER, 2005. Redox Site Confinement in Highly Unsymmetric Dimanganese Complexes. In: Inorganic Chemistry. 44(11), pp. 3863-3874. ISSN 0020-1669. Available under: doi: 10.1021/ic0503683

@article{Sheng2005-05-30Redox-13805, title={Redox Site Confinement in Highly Unsymmetric Dimanganese Complexes}, year={2005}, doi={10.1021/ic0503683}, number={11}, volume={44}, issn={0020-1669}, journal={Inorganic Chemistry}, pages={3863--3874}, author={Sheng, Tianlu and Dechert, Sebastian and Hyla-Kryspin, Isabella and Winter, Rainer and Meyer, Franc} }

<rdf:RDF xmlns:dcterms="" xmlns:dc="" xmlns:rdf="" xmlns:bibo="" xmlns:dspace="" xmlns:foaf="" xmlns:void="" xmlns:xsd="" > <rdf:Description rdf:about=""> <dc:language>eng</dc:language> <dc:creator>Winter, Rainer</dc:creator> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dcterms:hasPart rdf:resource=""/> <dcterms:abstract>A set of highly preorganized pyrazolate-bridged dimanganese complexes L(Mn)MnX have been prepared and structurally characterized. They can be described as hybrid organometallic/Werner-type systems that consist of a low-spin CpMn(I)(CO)2 subunit (Mn1) and a proximate tripodal tetradentate {N4} binding pocket accommodating a high-spin Mn(II) ion (Mn2), with Mn...Mn distances of approximately 4.3 A and different coligands bound to Mn2. Density functional theory (DFT) calculations (both the hybrid B3LYP and the pure BP86 functionals and the all-electron basis sets 6-311G and 6-311G*) confirm that the valence alpha and beta Kohn-Sham molecular orbitals (MOs) of these mixed-valent Mn(I)Mn(II) compounds have predominant Mn(3d) character and an almost perfectly localized nature: all five unpaired electrons are essentially localized at the Werner-type Mn2, whereas Mn1 possesses an effective closed-shell structure with the MOs of highest energy centered there. One-electron oxidation occurs in a clean process at approximately E(1/2) = -0.6 V (versus ferrocene/ferrocinium), giving the low-spin/high-spin Mn(II)Mn(II) species. UV/vis and IR spectroelectrochemistry as well as a detailed theoretical analysis reveal that the redox process takes place with strict site control at the organometallic subunit, while it does not significantly influence the spin and charge distribution on the Werner-type site. Positions and shifts of the nu(C[triple bond]O) absorptions are largely reproduced by the DFT calculations. These systems thus represent an exceptional example of the effect the unsymmetry of a dinucleating ligand scaffold has on the spin and charge distribution in homobimetallic complexes and might offer interesting prospects for the study of the cooperative effects of bimetallic arrays.</dcterms:abstract> <dc:date rdf:datatype="">2011-06-22T08:38:29Z</dc:date> <dc:contributor>Hyla-Kryspin, Isabella</dc:contributor> <dc:creator>Sheng, Tianlu</dc:creator> <dcterms:title>Redox Site Confinement in Highly Unsymmetric Dimanganese Complexes</dcterms:title> <dspace:isPartOfCollection rdf:resource=""/> <dc:contributor>Winter, Rainer</dc:contributor> <foaf:homepage rdf:resource="http://localhost:8080/jspui"/> <dcterms:rights rdf:resource=""/> <dc:creator>Hyla-Kryspin, Isabella</dc:creator> <dc:contributor>Dechert, Sebastian</dc:contributor> <bibo:uri rdf:resource=""/> <dcterms:available rdf:datatype="">2011-06-22T08:38:29Z</dcterms:available> <dc:creator>Meyer, Franc</dc:creator> <dcterms:bibliographicCitation>First publ. in: Inorganic Chemistry 44 (2005), 11, pp. 3863–3874</dcterms:bibliographicCitation> <dspace:hasBitstream rdf:resource=""/> <dcterms:issued>2005-05-30</dcterms:issued> <dc:contributor>Sheng, Tianlu</dc:contributor> <dc:creator>Dechert, Sebastian</dc:creator> <dc:rights>terms-of-use</dc:rights> <dc:contributor>Meyer, Franc</dc:contributor> <dcterms:isPartOf rdf:resource=""/> </rdf:Description> </rdf:RDF>

Downloads since Oct 1, 2014 (Information about access statistics)

Winter.pdf 130

This item appears in the following Collection(s)

Search KOPS


My Account