title: Extraction and coordination studies of a carbonyl-phosphine oxide scorpionate ligand with uranyl and lanthanide(III) nitrates: structural, spectroscopic and DFT characterization of the complexes.
abstract: Hybrid scorpionate ligand (OPPh2)2CHCH2C(O)Me (L) was synthesized and characterized by spectroscopic methods and X-ray diffraction. The selected coordination chemistry of L with UO2(NO3)2 and Ln(NO3)3 (Ln = La, Nd, Lu) has been evaluated. The isolated mono- and binuclear complexes, namely, [UO2(NO3)2L] (1), [{UO2(NO3)L}2(μ2-O2)]·EtOH (2), [La(NO3)3L2]·2.33MeCN (3), [Nd(NO3)3L2]·3MeCN (4), [Nd(NO3)2L2]+·(NO3)−·EtOH (5) and [Lu(NO3)3L2] (6) have been characterized by IR spectroscopy and elemental analysis. Single-crystal X-ray structures have been determined for complexes 1-5. Intramolecular intraligand π-stacking interactions between two phenyl fragments of the coordinated ligand(s) were observed in all complexes 1-5. The π-stacking interaction energy was estimated from Bader's AIM theory calculations performed at the DFT level. Solution properties have been examined using IR and multinuclear ((1)H, (13)C, and (31)P) NMR spectroscopy in CD3CN and CDCl3. Coordination modes of L vary with the coordination polyhedron of the metal and solvent nature showing many coordination modes: P(O),P(O), P(O),P(O),C(O), P(O),C(O), and P(O). Preliminary extraction studies of U(VI) and Ln(III) (Ln = La, Nd, Ho, Yb) from 3.75 M HNO3 into CHCl3 show that scorpionate L extracts f-block elements (especially uranium) better than its unmodified prototype (OPPh2)2CH2.
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., Moscow 119991, Russia.
authors.forename: Anna G
authors.initials: AG
authors.lastname: Matveeva
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., Moscow 119991, Russia.
authors.forename: Anna V
authors.initials: AV
authors.lastname: Vologzhanina
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., Moscow 119991, Russia.
authors.forename: Evgenii I
authors.initials: EI
authors.lastname: Goryunov
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., Moscow 119991, Russia.
authors.forename: Rinat R
authors.initials: RR
authors.lastname: Aysin
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., Moscow 119991, Russia.
authors.forename: Margarita P
authors.initials: MP
authors.lastname: Pasechnik
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., Moscow 119991, Russia.
authors.forename: Sergey V
authors.initials: SV
authors.lastname: Matveev
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., Moscow 119991, Russia.
authors.forename: Ivan A
authors.initials: IA
authors.lastname: Godovikov
authors.affiliation: OJSC United Chemical Company Uralchem, Presnenskaya nab. 6/2, Moscow, 123317 Russia. matveeva@ineos.ac.ru.
authors.forename: Alfiya M
authors.initials: AM
authors.lastname: Safiulina
authors.affiliation: Nesmeyanov Institute of Organoelement Compounds, Russian Academy of Sciences, 28 Vavilov Str., Moscow 119991, Russia.
authors.forename: Valery K
authors.initials: VK
authors.lastname: Brel