One-Electron oxidation of heterodinuclear organometallic compounds having polyphosphido bridges

Winter, Rainer F.; Geiger, William E.

One-Electron oxidation of heterodinuclear organometallic compounds having polyphosphido bridges

Dateien

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Datum

2003

Autor:innen

Winter, Rainer F.

Geiger, William E.

Open Access-Veröffentlichung

Open Access Green

Sammlungen

Chemie

Publikationstyp

Zeitschriftenartikel

Publikationsstatus

Published

Erschienen in

Organometallics. 2003, 22(9), pp. 1948-1952. ISSN 0276-7333. Available under: doi: 10.1021/om020778o

Zusammenfassung

The electrochemical behavior of several heterometallic compounds having polyphosphido bridges has been investigated. Reversible one-electron oxidations were observed for CpFe(P5)TaCp‘‘ (2), CpFe(P5)[Ir2(CO)2Cp2] (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.

Fachgebiet (DDC)

540 Chemie

Zitieren

ISO 690

WINTER, Rainer F., William E. GEIGER, 2003. One-Electron oxidation of heterodinuclear organometallic compounds having polyphosphido bridges. In: Organometallics. 2003, 22(9), pp. 1948-1952. ISSN 0276-7333. Available under: doi: 10.1021/om020778o

BibTex

@article{Winter2003OneEl-13862,
  year={2003},
  doi={10.1021/om020778o},
  title={One-Electron oxidation of heterodinuclear organometallic compounds having polyphosphido bridges},
  number={9},
  volume={22},
  issn={0276-7333},
  journal={Organometallics},
  pages={1948--1952},
  author={Winter, Rainer F. and Geiger, William E.}
}

RDF

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    <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>
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