Synthesis and characterization of thorium and uranium tetraphenylimidophosphinate complexes. Crystal and molecular structures of Th(tpip)(4), U(tpip)(4) and UCl(tpip)(3)

摘要

Tetra(tetraphenylimidophosphinato)thorium, Th(tpip)(4) (1), was obtained from Th(NO4). 4H(2)O and Ktpip in aqueous medium. The analogous uranium compound, U(tpip)(4) (2), has been prepared by reacting UCl4 with Ktpip in a 1:4 stoichiometric ratio, either in THF or in aqueous solution. X-ray diffraction analysis showed that compounds 1 and 2 were isostructural. The metal center is eight-coordinate by way of four bidentate tetraphenylimidophosphinate ligands in a square antiprismatic configuration. UCl(tpip)(3) (3) has been isolated from the reaction of uranium tetrachloride with 3 equiv. of Ktpip in aqueous solution. When this reaction was run in THF both compounds, U(tpip)(4) and UCl(tpip)(3), were obtained. The molecular structure of 3 has been determined by X-ray crystallography. The uranium atom is seven-coordinate in a pentagonal bipyramidal configuration. These compounds were also characterized by infrared and H-1 and P-31 NMR spectroscopies. (C) 2000 Elsevier Science Ltd. All rights reserved. [References: 21]