Chemistry of Trivalent Uranium Metallocenes: Electron-Transfer Reactions. Synthesis and Characterization of [(MeC5H4)3U]2E (E = S, Se, Te) and the Crystal Structures of [(MeC5H4)3U]2S and (MeC5H4)3UOPPh3

John G. Brennan, Richard A. Andersen, Allan Zalkin

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Abstract

The trivalent uranium metallocene (MeC5H4)3U.THF reacts with COS, SPPh3, SePPh3, or TeP(n-Bu)3 to form the bridging chalcogenide complexes [(MeC5H4)3U]2E, where E is S, Se, or Te. Crystals of [(MeC5H4)3U]2S are monoclinic, P21/c, with a = 19.740 (6) Å, b = 8.302 (3) Å, c = 21.602 (4) Å, and β = 97.28 (3)° at 23 °C; for Z = 4 the calculated density is 1.920 g/cm3. The structure was refined by full-matrix least squares to a conventional R factor of 0.053 by using 2061 data with F2> 2σ(F2). The average U—C distance is 2.77 ± 0.06 A, the U—S distance is 2.60 (1) A, and the U-S-U angle is 164.9 (5)°. Triphenylphosphine oxide does not behave in a similar fashion; the trivalent uranium coordination complex (MeC5H4)3UOPPh3 is instead isolated. Crystals of (MeC5H4)3UOPPh3 are monoclinic, P21/n, with a = 16.268 (3) Å, b = 17.948 (3) Å, c = 10.900 (2) Å, and β= 105.01 (2)° at 23 °C; for Z = 4 the calculated density is 1.628 g/cm3. The structure was refined by full-matrix least squares to a conventional R factor of 0.028 [2427 data, F2> 2σ(F2)]. The average U-C distance is 2.82 ± 0.04 Å, the U-O distance is 2.389 (6) Å, and the U—O—P angle is 162.8 (4)°.

Original languageEnglish (US)
Pages (from-to)1761-1765
Number of pages5
JournalInorganic Chemistry
Volume25
Issue number11
DOIs
StatePublished - May 1 1986
Externally publishedYes

All Science Journal Classification (ASJC) codes

  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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