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One-Electron oxidation of heterodinuclear organometallic compounds having polyphosphido bridges

One-Electron oxidation of heterodinuclear organometallic compounds having polyphosphido bridges

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WINTER, Rainer, William E. GEIGER, 2003. One-Electron oxidation of heterodinuclear organometallic compounds having polyphosphido bridges. In: Organometallics. 22(9), pp. 1948-1952. ISSN 0276-7333

@article{Winter2003One-E-13862, title={One-Electron oxidation of heterodinuclear organometallic compounds having polyphosphido bridges}, year={2003}, doi={10.1021/om020778o}, number={9}, volume={22}, issn={0276-7333}, journal={Organometallics}, pages={1948--1952}, author={Winter, Rainer and Geiger, William E.} }

<rdf:RDF xmlns:rdf="http://www.w3.org/1999/02/22-rdf-syntax-ns#" xmlns:bibo="http://purl.org/ontology/bibo/" xmlns:dc="http://purl.org/dc/elements/1.1/" xmlns:dcterms="http://purl.org/dc/terms/" xmlns:xsd="http://www.w3.org/2001/XMLSchema#" > <rdf:Description rdf:about="https://kops.uni-konstanz.de/rdf/resource/123456789/13862"> <dcterms:rights rdf:resource="http://nbn-resolving.org/urn:nbn:de:bsz:352-20140905103605204-4002607-1"/> <bibo:uri rdf:resource="http://kops.uni-konstanz.de/handle/123456789/13862"/> <dc:rights>deposit-license</dc:rights> <dc:language>eng</dc:language> <dcterms:bibliographicCitation>First publ. in: Organometallics 22 (2003), 9, pp. 1948–1952</dcterms:bibliographicCitation> <dcterms:title>One-Electron oxidation of heterodinuclear organometallic compounds having polyphosphido bridges</dcterms:title> <dcterms:available rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-06-28T10:04:44Z</dcterms:available> <dc:creator>Geiger, William E.</dc:creator> <dc:contributor>Geiger, William E.</dc:contributor> <dc:contributor>Winter, Rainer</dc:contributor> <dc:date rdf:datatype="http://www.w3.org/2001/XMLSchema#dateTime">2011-06-28T10:04:44Z</dc:date> <dcterms:abstract xml:lang="eng">The electrochemical behavior of several heterometallic compounds having polyphosphido bridges has been investigated. Reversible one-electron oxidations were observed for Cp*Fe(P5)TaCp‘‘ (2), Cp*Fe(P5)[Ir2(CO)2Cp*2] (3), and Cp‘‘‘2Co2(P2)2 (4) (Cp* = C5M5, Cp‘‘ = C5H3tBu2, Cp‘‘‘ = C5H2tBu3). In contrast to the pseudo-sandwich polyphosphido complex Cp*FeP5 (1), compounds 2−4 undergo very facile oxidations and the corresponding monocations may be generated by bulk electrolysis or by reaction with ferrocenium ion. E1/2 values (vs Cp2Fe0/+) for the oxidations are −0.24 V for 2, −0.58 V for 3, and −0.33 V for 4 in CH2Cl2/0.1 M [NBu4][PF6], in contrast to 0.57 V for 1. Although ESR spectra of 2+ display hyperfine coupling to 181Ta, the SOMO appears to have only minor Ta character. IR spectroelectrochemistry of the 3/3+ couple reveals an increase of νCO of only 11 cm-1, indicating that the oxidation of 3 also occurs predominantly at the iron center. The fact that the Fe-based oxidations of 2 and 3 are more negative than that of 1 by ca. 0.8 and 1.15 V, respectively, is ascribed to differences in the iron formal oxidation state which arise from the structural variations of the P5 bridging groups.</dcterms:abstract> <dc:creator>Winter, Rainer</dc:creator> <dcterms:issued>2003</dcterms:issued> </rdf:Description> </rdf:RDF>

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