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One-Electron oxidation of heterodinuclear organometallic compounds having polyphosphido bridges

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2003

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Geiger, William E.

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

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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.

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540 Chemie

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ISO 690WINTER, 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.}
}
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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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