Synthesis of Trapen Ligand-Based U(IV) and Th(IV) 2-Phosphaethynolate Complexes and Comparison of Covalency with Corresponding Ti(IV) Analogues

Abstract

The involvement of the 2-phosphaethynolate anion species with ambident nucleophilic properties serves as an essential protocol for synthesizing oxygen-bound or phosphorus-bound complexes. This work mainly describes the synthesis and characterization of U, Th, and Ti phosphaethynolate complexes featuring a preferential O-coordination fashion. Among these complexes, the first examples of a Ti(IV)-OCP complex 3A, Th(IV)-OCP complex 3B, and U(IV)-OCP complex 3C were assembled by a salt metathesis reaction between M(Trapen TMS )(Cl) (M = Ti, Th, U) and NaOCP(dioxane) 2.5 and were all crystallographically characterized. The structural similarity of this series of phosphaethynolate complexes allows us to compare the bonding properties of d-and f-block elements in the corresponding compounds. The well-established density functional theory (DFT) computational method was employed to explore the electronic structures and covalency in M−O bonding, and the results showed a consistent pattern. The calculation result showed that 2-phosphaethynolate complexes exhibited the covalency trend of U−O > Th−O > Ti−O due to the involvement of 5f orbitals.

4f/5d Hybridization Induced Single-Electron Delocalization in an Azide-Bridged Dicerium Complex

“…Complex 1 , [(Trapen TMS )­Ce­(THF)] (Trapen = tris (2-aminobenzyl)­amine; TMS = SiMe 3 ), was prepared with satisfactory yield by the reaction of [(Trapen TMS )­(Li) 3 ] − with CeCl 3 (THF) 2 in THF at −30 °C, following an analogous route previously reported for (TriNO x )­Ce­(THF) (Scheme ). The molecular structure of complex 1 was characterized by single-crystal X-ray diffraction and multinuclear NMR spectroscopy.…”

Study on the affinity sites of cadmium's binding to ligands by thermodynamics and nuclear magnetic resonance spectroscopy

“…Currently, there are several screening methods for ion-imprinted polymer functional monomers: [29][30][31] (1) ultraviolet spectroscopy, which is the most commonly used method for screening ion-imprinted functional monomers; (2) ion simulation technology, where computer simulation soware is used to simulate the interaction forces between template ions and some functional monomers and to calculate the magnitude of these forces, enabling the best functional monomers to be selected; (3) nuclear magnetic resonance spectroscopy (NMR), which can also be used to screen functional monomers. [32][33][34][35][36] However, these methods have some limitations. For example, ultraviolet spectroscopy is mainly suitable for the screening of functional monomers containing special functional groups; some substances without absorption peaks in the ultraviolet range cannot be screened by this method.…”

Modulating the Magnetic Dynamics of Five‐Coordinate DyIII Single‐Molecule Magnets by the Substitution Effect on the Axial Ligand

“…Moreover, some related studies have shown that tripod ligands have advantages in the construction of fivecoordinate triangular bipyramidal complexes. [27][28][29][30][31][32] Inspired by previous work, we were interested in preparing a new class of five-coordinate triangular bipyramid mononuclear Dy III -based SIMs with local D 3h symmetry. For deeper understanding of magneto-structural correlation and detailed theoretical elucidations of the dynamic magnetic behaviors in five-coordinate Dy III SIMs.…”