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)°.
All Science Journal Classification (ASJC) codes
- Physical and Theoretical Chemistry
- Inorganic Chemistry