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Synthesis and crystal structures of rhodium acetate paddle‐wheel complexes with anchor group‐functionalized and hydrogen bond‐supported axial ligands

Synthesis and crystal structures of rhodium acetate paddle‐wheel complexes with anchor group‐functionalized and hydrogen bond‐supported axial ligands

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WINTER, Rainer Friedrich, André MANG, Michael LINSEIS, 2022. Synthesis and crystal structures of rhodium acetate paddle‐wheel complexes with anchor group‐functionalized and hydrogen bond‐supported axial ligands. In: Zeitschrift für anorganische und allgemeine Chemie (ZAAC). Wiley. ISSN 0863-1786. eISSN 1521-3749. Available under: doi: 10.1002/zaac.202200199

@article{Winter2022Synth-58277, title={Synthesis and crystal structures of rhodium acetate paddle‐wheel complexes with anchor group‐functionalized and hydrogen bond‐supported axial ligands}, year={2022}, doi={10.1002/zaac.202200199}, issn={0863-1786}, journal={Zeitschrift für anorganische und allgemeine Chemie (ZAAC)}, author={Winter, Rainer Friedrich and Mang, André and Linseis, Michael} }

<rdf:RDF xmlns:dcterms="http://purl.org/dc/terms/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dspace="http://digital-repositories.org/ontologies/dspace/0.1.0#" xmlns:foaf="http://xmlns.com/foaf/0.1/" xmlns:void="http://rdfs.org/ns/void#" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/58277"> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2022-08-12T07:12:09Z</dc:date> <bibo:uri rdf:resource="https://kops.uni-konstanz.de/handle/123456789/58277"/> <dcterms:rights rdf:resource="https://rightsstatements.org/page/InC/1.0/"/> <dc:creator>Linseis, Michael</dc:creator> <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dc:creator>Winter, Rainer Friedrich</dc:creator> <dc:contributor>Mang, André</dc:contributor> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dc:creator>Mang, André</dc:creator> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2022-08-12T07:12:09Z</dcterms:available> <dc:contributor>Linseis, Michael</dc:contributor> <dc:language>eng</dc:language> <foaf:homepage rdf:resource="http://localhost:8080/jspui"/> <dcterms:issued>2022</dcterms:issued> <dc:rights>terms-of-use</dc:rights> <dc:contributor>Winter, Rainer Friedrich</dc:contributor> <dcterms:title>Synthesis and crystal structures of rhodium acetate paddle‐wheel complexes with anchor group‐functionalized and hydrogen bond‐supported axial ligands</dcterms:title> <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dcterms:abstract xml:lang="eng">We report the synthesis and X-ray structures of four Rh 2 (O 2 Ac) 4 (L Ax ) 2 (OAc = acteate, CH 3 COO - ) paddle-wheel complexes ( C1 - C4 ) with methylthio-modified axial ligands L Ax derived from benzamidine ( L1 ), anilinopyrimidine ( L2 ) or isothiourea ( L3 , L4 ) that are capable of forming N‑H×××O hydrogen bonds to the equatorially bridging acetate ligands. This was done with the aim to suppress dissociation of the axial ligands and to make the complexes amenable to single-molecule conductance measurements in a scanning tunneling microscope break-junction (STM-BJ) setup. The characteristic spectroscopic features (NMR, IR, vis), crystal structures, the hydrogen-bonding motifs and a DFT-based screening of their frontier molecular orbitals are presented. Our calculations suggest that hydrogen-bonding stabilizes axial ligand binding by 20kJ/mol to 30 kJ/mol and that the HOMO of the rhodium paddle-wheels is closer to the Au Fermi level than the LUMO, so that the rhodium paddle-wheels are expected to constitute hole conductors.</dcterms:abstract> </rdf:Description> </rdf:RDF>

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