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

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• 作者：Paul T. Morse^a ; Richard J. Staples^b ; Shannon M. Biros^a ; ^{biross@gvsu.edu" class="auth_mail" title="E-mail the corresponding author}
• 关键词：Actinide ; Crystal structure ; NMR ; Phosphine oxide ; High denticity complex
• 刊名：Polyhedron
• 出版年：2016
• 出版时间：16 August 2016
• 年：2016
• 卷：114
• 期：Complete
• 页码：2-12
• 全文大小：3355 K

文摘

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 polymorphs 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 CHCl₃. Analysis of CD₃OD and CDCl₃ solutions of this complex using ¹H and ³¹P NMR reveals that ligand exchange rates are fast on the NMR time scale in methanol-d₄, 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.