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Synthesis and Crystal Structure of Novel 1,3-Heterobinuclear Complexes with an Unusual Cyclic C4R3 Bridging Ligand

Synthesis and Crystal Structure of Novel 1,3-Heterobinuclear Complexes with an Unusual Cyclic C4R3 Bridging Ligand

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FISCHER, Helmut, Frédéric LEROUX, Gerhard ROTH, Rüdiger STUMPF, 1996. Synthesis and Crystal Structure of Novel 1,3-Heterobinuclear Complexes with an Unusual Cyclic C4R3 Bridging Ligand. In: Organometallics. 15(17), pp. 3723-3731. ISSN 0276-7333. eISSN 1520-6041. Available under: doi: 10.1021/om960278t

@article{Fischer1996Synth-23059, title={Synthesis and Crystal Structure of Novel 1,3-Heterobinuclear Complexes with an Unusual Cyclic C4R3 Bridging Ligand}, year={1996}, doi={10.1021/om960278t}, number={17}, volume={15}, issn={0276-7333}, journal={Organometallics}, pages={3723--3731}, author={Fischer, Helmut and Leroux, Frédéric and Roth, Gerhard and Stumpf, Rüdiger} }

<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/123456789/23059"> <void:sparqlEndpoint rdf:resource="http://localhost/fuseki/dspace/sparql"/> <dc:creator>Roth, Gerhard</dc:creator> <foaf:homepage rdf:resource="http://localhost:8080/jspui"/> <dc:rights>terms-of-use</dc:rights> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/23059"/> <dc:creator>Stumpf, Rüdiger</dc:creator> <dcterms:isPartOf rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dcterms:bibliographicCitation>Organometallics ; 15 (1996), 17. - S. 3723–3731</dcterms:bibliographicCitation> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-06-13T08:34:00Z</dcterms:available> <dc:contributor>Roth, Gerhard</dc:contributor> <dc:language>eng</dc:language> <dc:creator>Fischer, Helmut</dc:creator> <dc:creator>Leroux, Frédéric</dc:creator> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2013-06-13T08:34:00Z</dc:date> <dcterms:title>Synthesis and Crystal Structure of Novel 1,3-Heterobinuclear Complexes with an Unusual Cyclic C4R3 Bridging Ligand</dcterms:title> <dspace:isPartOfCollection rdf:resource="https://kops.uni-konstanz.de/rdf/resource/123456789/29"/> <dcterms:abstract xml:lang="eng">Pentacarbonyl(dimethylvinylidene)chromium, [(CO)5CrCCMe2] (1), reacts with the alkynyl complexes [Cp(CO)2FeCCR] (4a−e; R = nBu (a), Me (b), Ph (c), C6H4NO2-p (d), COOMe (e)), [Cp(CO){P(OMe)3}FeCCnBu] (6), [Cp(CO){PPh3}FeCCnBu] (8), and [Cp(PEt3)NiCCnBu] (19) by cycloaddition of the CC bond of the alkynyl complexes to the CC bond of 1 to give [(CO)5Cr C CR C(CMe2) Fe(CO)2Cp] (5a−e), [(CO)5Cr C C(nBu) C(CMe2) Fe(CO){P(OMe)3}Cp] (7), [(CO)5Cr C C(nBu) C(CMe2) Fe(CO){PPh3}Cp] (9), and [(CO)5Cr C C(nBu) C(CMe2) Ni(PEt3)Cp] (20), respectively. The analogous reaction of [(CO)5CrCC(CH2)5] (2) with 4a and 6 affords complexes with a spirocyclic bridging ligand:  [(CO)5Cr C C(nBu) C{C(CH2)5} Fe(CO)2Cp] (10) and [(CO)5Cr C C(nBu) C{C(CH2)5} Fe(CO){P(OMe)3}Cp] (11). Cycloaddition of 4a to [(CO)5CrCCPh2] (3) yields [(CO)5Cr C C(nBu) C(CPh2) Fe(CO)2Cp] (12). The spectroscopic data of these novel 1,3-heterobinuclear complexes indicate the delocalized π-system Cr C C C M (M = Fe, Ni). X-ray structural analyses of the compounds 5e, 10, and 11 reveal a “butterfly” conformation. The puckering angle of the four-membered ring is 160.0° (5e), 143.9° (10), and 144.9° (11). Both C(sp2)−C(sp2) bonds are almost equal in length. All complexes exhibit negative solvatochromic behavior. The extent of the solvatochromic effect is strongly influenced by the substituents at C-2 and C-4 of the ring.</dcterms:abstract> <dc:contributor>Leroux, Frédéric</dc:contributor> <dcterms:rights rdf:resource="https://kops.uni-konstanz.de/page/termsofuse"/> <dc:contributor>Stumpf, Rüdiger</dc:contributor> <dc:contributor>Fischer, Helmut</dc:contributor> <dcterms:issued>1996</dcterms:issued> </rdf:Description> </rdf:RDF>

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