Synthesis of chelating tertiary phosphine oxides via palladium-catalysed C–P bond formation

Zakirova, Gladis G.; Mladentsev, Dmitrii Yu.; Borisova, Nataliya E.

doi:10.1016/j.tetlet.2017.07.055

Cited by 22 publications

(9 citation statements)

References 37 publications

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“…Nevertheless, some disadvantages like poor acid resistance and slow stripping kinetics of BTP ligands still limited their further industrial application. In 2019, Matveev et al 15 adopted the P−C synthesis method of Zakirova et al 16 with reference to the binary neutral organophosphorus compound (BNOC), which was originally used for the extraction of transuranic elements. Two phosphoryl groups were connected to a pyridine ring to obtain the ligand Ph 2 PyPO (Figure 1), which was applied in selectively extracted trivalent actinide over lanthanide elements.…”

Section: ■ Introductionmentioning

confidence: 99%

Separation and Complexation of Trivalent Actinides and Lanthanides by Two Novel Asymmetric N,O-Hybrid Pyridyl Ligands: A Combination of Phosphoryl and Triazinyl Groups

Miao

Yang

et al. 2022

Inorg. Chem.

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Two novel asymmetric hard–soft combined ligands, diphenyl(6-(5,9,9-trimethyl-5,6,7,8-tetrahydro-5,8-methanobenzo-[1,2,4]triazin-3-yl)pyridin-2-yl)phosphine oxide (Ph2-MTP) and butylphenyl(6-(5,9,9-trimethyl-5,6,7,8-tetrahydro-5,8-methanobenzo-[1,2,4]triazin-3-yl)pyridin-2-yl)phosphine oxide (BuPh-MTP), were designed based on the combination of the nature of phosphoryl and triazinyl groups for the selective extraction of trivalent minor actinides from lanthanides. The synthesis of these two ligands and their solvent extraction and complexation behaviors with Am(III) and typical lanthanides were investigated using UV–vis and time-resolved fluorescence spectrophotometry, 1H/31P NMR spectrometry, single-crystal X-ray diffraction, and DFT calculation methods. Solvent extraction experiments showed that both the ligands had strong extraction ability and high selectivity toward Am(III) over Eu(III) from the highly acidic HNO3 solution. The separation factors (SF Am/Eu) of these two ligands ranged from 17 to 26, with the concentrations of HNO3 increasing from 1.0 to 4.0 M. Slope analysis showed that the 3:1 ligand/metal complex was the prevailing species formed during extraction. The formation of the 3:1 ratio of the species of these two ligands with lanthanides was also identified by UV–vis spectrophotometry and single crystallography methods. The stability constants for the formation of the 1:3 complexes of Ph2-MTP and BuPh-MTP with Nd(III) were determined as 7.06 ± 0.015 and 6.67 ± 0.007, respectively. The geometric structures of the 1:3 complexes were clearly illustrated using the single-crystal X-ray diffraction technique and DFT theoretical calculation. This work provides an effective strategy to design new asymmetric hard–soft mixed actinide extractants by combining two different functional groups in one ligand, and the interaction mechanism between the functional groups and metal ions needs to be further investigated.

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Section: ■ Introductionmentioning

confidence: 99%

Separation and Complexation of Trivalent Actinides and Lanthanides by Two Novel Asymmetric N,O-Hybrid Pyridyl Ligands: A Combination of Phosphoryl and Triazinyl Groups

Miao

Yang

et al. 2022

Inorg. Chem.

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“…Other commercially obtained chemical reagents like Cs 2 CO 3 , anhydrous diethyl ether, CH 3 CN, CH 3 OH, dry toluene, Pd(OAc) 2 , 1,1′-bis(diphenylphosphino)ferrocene (dppf), ethyl-phenylphosphinate, diphenylphosphine oxide, and 2,9-dichloro-1,10-phenanthroline for the synthesis experiments are all analytical grade. Ph 2 -BPPhen was synthesized using a palladium-catalyzed C–P cross-coupling reaction between 2,9-dichloro-1,10-phenanthroline and diphenylphosphine oxide according to the reported procedures. , Ph 2 -BPPhen, 1 H NMR (500 MHz, CD 3 OD/CDCl 3 (10/3, v/v), 295 K): δ = 7.30 ppm (m, 8H, −Ar– H ), 7.51 ppm (t, 4H, −Ar– H ), 7.95 ppm (m, 8H, −Ar– H ), 8.07 ppm (s, 2H, −Phen– H ), 8.59 ppm (dd, 2H, −Phen- H ); 8.64 ppm (dd, 2H, −Phen– H ); 31 P NMR (121 MHz, CD 3 OD/CDCl 3 (10/3, v/v), 295 K): δ = 22.55 ppm (s, 1P).…”

Section: Methodsmentioning

confidence: 99%

Unfolding the Extraction and Complexation Behaviors of Trivalent f-Block Elements by a Tetradentate N,O-Hybrid Phenanthroline Derived Phosphine Oxide Ligand

Yang

Wang

et al. 2021

Inorg. Chem.

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In this work, a tetradentate N,O-hybrid 2,9-bis(diphenylphosphine oxide)-1,10-phenanthroline (Ph2-BPPhen) ligand was studied for the coextraction of trivalent f-block elements from nitric acid media. The extraction as well as the complexation behaviors of Ph2-BPPhen with f-block elements were thoroughly investigated using 31P and 1H NMR spectrometry, UV–vis spectrophotometry, single crystal X-ray diffraction, and density functional theoretical (DFT) calculation. Ph2-BPPhen exhibits remarkably extraction ability for both Am(III) and Eu(III) and more than 99.5% of Am(III) and Eu(III) were extracted from 1.0 M HNO3 solution. Slope analysis suggests that both 2:1 and 1:1 ligand/metal complexes were probably formed during the extraction. The 1:1 and 2:1 Ln(III) complexes with Ph2-BPPhen were also identified in CH3OH solution by NMR spectrometry, and the stability constants were determined via UV–vis spectrophotometry. Structures of the 1:1 Eu(Ph2-BPPhen)(NO3)3 and Am(Ph2-BPPhen)(NO3)3 complexes were further elucidated by single X-ray crystallography and DFT calculations. The higher extractability of Ph2-BPPhen toward trivalent Am(III) and Eu(III) compared with the previously reported phenanthroline-derived amide and phosphonate ligands was attributed to the stronger affinity of the −PO(R)2 group to metal ions. The results from this work indicate that the N,O-hybrid 1,10-phenanthroline derived phosphine oxide ligand can serve as a new and promising candidate for coextraction of trivalent f-block elements in the treatment of nuclear waste.

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“…The palladium‐catalyzed reaction between pyridine‐type dichlorides and tert ‐butyl(phenyl) phosphine/diphenylphosphine oxides was reported by Zakirova et al . in 2017 [46] . Sterically hindered phosphines were synthesized successfully from the corresponding heteroaryl chlorides than the corresponding bromides or iodides.…”

Section: Phosphorus Coupling Partnersmentioning

confidence: 99%

Palladium‐ Catalyzed C−P Bond Forming Reactions: An Overview

Kanchana¹,

Diana²,

Mathew³

et al. 2021

ChemistrySelect

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Transition metal catalyzed synthesis of organo‐phosphorus compounds show rapid advances. Due to the powerful bond‐forming ability under mild reaction conditions and wide functional group tolerance made palladium‐catalyzed reactions an inevitable tool for the synthesis of various structurally diversed complex molecules. This review is an account of palladium‐catalyzed Carbon‐Phosphorous bond forming reactions. For proving an insight into the synthetic and mechanistic knowledge of its chemistry some of the mechanisms of this type of catalysis are also added. This review focuses on the recent advances in Palladium‐catalyzed C−P bond forming reactions and covers literature from 2001 to 2020.

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Synthesis of chelating tertiary phosphine oxides via palladium-catalysed C–P bond formation

Cited by 22 publications

References 37 publications

Separation and Complexation of Trivalent Actinides and Lanthanides by Two Novel Asymmetric N,O-Hybrid Pyridyl Ligands: A Combination of Phosphoryl and Triazinyl Groups

Separation and Complexation of Trivalent Actinides and Lanthanides by Two Novel Asymmetric N,O-Hybrid Pyridyl Ligands: A Combination of Phosphoryl and Triazinyl Groups

Unfolding the Extraction and Complexation Behaviors of Trivalent f-Block Elements by a Tetradentate N,O-Hybrid Phenanthroline Derived Phosphine Oxide Ligand

Palladium‐ Catalyzed C−P Bond Forming Reactions: An Overview

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