A series of bis(η-cyclopentadienyl)uranium(III) dichloro-bridged-alkali-metal and dihalogenobis(η-cyclopentadienyl)uranate(III) complexes: single-crystal X-ray structure determination of [UCp″2(µ-Cl)2Li(pmdeta)] and [PPh4][UCp″2Cl2][Cp″=η-C5H3(SiMe3)2-1,3, pmdeta =(Me2NCH2CH2)2NMe]
Abstract
Reduction of [UCp″2Cl2] with either LiBun or Na–Hg in presence of the appropriate ligand L yields [UCp″2(µ-Cl)2M(L)n][M = Li or Na, Ln=(thf)2 or tmeda: or M = Li and Ln= pmdeta (5)], while addition of LiX in thf or [PPh4]X in PhMe to [{UCp″2(µ-Cl)}2] gives [UCp″2(µ-Cl)(µ-X)Li(thf)2] or [PPh4][UCp″2(Cl)X][X = Cl (7) or Br]; X-ray and 1H n.m.r. data on complexes (5) and (7) are compared with those for three other bis(η-cyclopentadienyl)-uranium(III or IV) or -uranate(III) chlorides having 2 p″s and 2 ls around U[Cp″=η-C5H3(SiMe3)2-1,3; thf = OC4H8, tmeda =(Me2NCH2)2; pmdeta =(Me2NCH2CH2)2NMe)].