Th(IV) complexes with cis-ethylenebis(diphenylphosphine oxide): X-ray structures and NMR solution studies

摘要

The complexation of Th(NO3)(4) with the rigid diphosphoryl ligand cis-ethylenebis(diphenylphosphine oxide) has been investigated using X-ray crystallography, IR, NMR and CHN analysis. Three crystal poly morphs were grown out of methanolic solution where the 1:3 Th(IV)-ligand complex is ten-coordinate, and the metal is bound by three bidentate ligands and two nitrato groups. An additional metal-ligand complex with similar geometry was also grown from the non-coordinating solvent CHCI3. Analysis of CD3OD and CDCI3 solutions of this complex using H-1 and P-31 NMR reveals that ligand exchange rates are fast on the NMR time scale in methanol-d(4), and slow on the NMR time scale in chloroform-d. Further, three additional crystal structures are reported describing the 1:1 and 1:2 Th(IV)-ligand complex, the 1:3 Th(IV)-ligand complex with an extra aqua ligand, and a serendipitous 1:3 Th(IV)-ligand structure where one ligand bears an epoxide. Published by Elsevier Ltd.