Coordination and extraction of lanthanides(III) with tripodal ligands on the triphenylphosphine oxide platform: Effect of uncoordinating substituents

Матвеева, А. Г.; Kudryavtsev, I. Yu.; Пасечник, М. П.; Вологжанина, Анна В.; Баулина, Т. В.; Vavina, Anna V.; Sukat, Georgiy Ya.; Матвеев, С. В.; Godovikov, Ivan A.; Туранов, А. Н.; Карандашев, В. К.; Brel, V. K.

doi:10.1016/j.poly.2017.12.025

Cited by 28 publications

(7 citation statements)

References 45 publications

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“…Такі полідентатні ліганди можуть зв'язувати іони металу ефективніше, ніж аналогічні моноклешневі сполуки [9], тому привернули значну увагу дослідників і знайшли застосування в різних сферах досліджень, включаючи молекулярний каталіз [10], каталітичну полімеризацію [11], розробку датчиків та оптичних молекулярних вимикачів [12]. Сполуки такого типу знаходять застосування у медичній візуалізації та терапії, для трансмембранного транспорту, як екстрагенти, для проектування одномолекулярних магнітів [13].…”

Section: = N(ch 2 Ch 2 N(h)c(o)n(h)p(o)(och 3 ) 2 ) 3 і на його основі одержано та виділено в кристалічному стані ряд координаційних сполunclassified

SYNTHESIS AND SPECTRAL PROPERTIES OF LANTANIDE COMPLEXES WITH A NEW TRIPODAL TRIS-CHELATING CAPh LIGAND

Strugatska

Olyshevets

Оvchynnikov

et al. 2018

Bull. T. Shevchenko Nat. Univ. Kyiv. Chem.

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A new tripodal tris-chelating carbacylamidophosphate (CAPh) ligand (H3L = N(CH2CH2N(H)C(O)N(H)P(O)(OCH3)2)3) has been synthesized and a series of coordination compounds of general formula LnL (where Ln = La, Nd, Eu, Tb) based on this ligand has been obtained and isolated in the crystalline state. The resulting compounds have been investigated by the means of thermal gravimetric analysis, 1H NMR, IR and UV-Vis absorption spectroscopy. The ligand and all complexes are soluble in water, poorly soluble in methanol and isopropanol, insoluble in nonpolar solvents. It was found, that each Ln(III) ion of the complexes under consideration is bonded with oxygen atoms belonging to the phosphoryl and carboxyl groups of three bidentate chelated coordinating arms of the ligand (six lanthanide-oxygen bonds totally). In the 1H NMR spectrum of lanthanum coordination compound (LnL) all signals are shifted in the region of a strong field compared to analogous signals in the respective H3L spectrum, which can be explained by the redistribution of electronic density in the ligand due to deprotonation. The fine structure of the supersensitive transitions in the electronic spectrum of the synthesized neodymium complex proves in favor of the coordination number 8. In the region of 4I9/2 → 2P1/2 transition (425–435 nm) a single absorption band is observed, indicating the presence of only one absorption center. The thermal stability of NdL complex has been investigated and the presence of two coordinated water molecules in the synthesized complexes has been established. Thus, coordination number of lanthanide ions is equal to eight (coordination formula [LnL(H2O)2]) which is in agreement with electronic spectroscopy results. Based on the data of the TGA for the coordination compound [NdL(H2O)2] one can conclude that significant mass loss occurs in one step. The complex compound begins to decompose above 200°C. Considerable mass loss continues to a temperature of 380–400°С. The DTA curve shows an exothermic effect at a temperature of 287°C, which can be connected with the oxidation processes.

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SYNTHESIS AND SPECTRAL PROPERTIES OF LANTANIDE COMPLEXES WITH A NEW TRIPODAL TRIS-CHELATING CAPh LIGAND

Strugatska

Olyshevets

Оvchynnikov

et al. 2018

Bull. T. Shevchenko Nat. Univ. Kyiv. Chem.

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“…Molecules of ortho ‐substituted triarylphosphine oxides (2‐RC 6 H 4 ) 3 PO with small substituents (R = OH, Me, CH(Me)NMe 2 , CH=NCHMePh, and CH 2 N(O)Me 2 ) are known to have in crystalline state 3‐UP conformation where these substituents are on the same side as the P=O group (), which is likely to provide minimal internal strain in the molecule. However, 2‐UP conformation is also known for phosphine oxides (2‐RC 6 H 4 ) 3 PO with flexible long‐chain substituents (R = OCH 2 CH 2 OMe and OCH 2 CONBu 2 ). In this conformation, two ortho substituents are oriented to the same direction as the P=O group, while the third substituent is directed to the opposite side ().…”

Section: Introductionmentioning

confidence: 99%

“…Furthermore, metal cation can attract side groups with donor atoms upon coordination. For example, (2‐RC 6 H 4 ) 3 PO with R = OCH 2 CONMe 2 in crystal has 1‐UP conformation where one arm is up while two arms are down with respect to the P=O group, but the ligand adopts 2‐UP conformation in crystalline neodymium complex when the P=O and two C=O groups are coordinated to the metal …”

Section: Introductionmentioning

confidence: 99%

“…Tris(2‐hydroxyphenyl)phosphine oxide ( 1 ) is a convenient synthetically available ancestor compound for the synthesis of tripodal ligands of different structure, which may be suitable for the selective binding of d ‐block and f ‐block elements . To construct such ligands, we need to develop convenient synthetic approaches to form side arms of prescribed structure and gain precursors containing in the side arms different functional groups that can be readily transformed into desired donor fragments.…”

Section: Introductionmentioning

confidence: 99%

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Synthesis and molecular structure of functionalized tris[2‐(4′‐substituted butoxyphenyl)]phosphine oxides as precursors of tripodal ligands

Баулина

Kudryavtsev

Smol’yakov

et al. 2018

Heteroatom Chemistry

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A series of tris[2‐(4′‐substituted butoxyphenyl)]phosphine oxides [2‐X(CH2)4OC6H4]3PO (X = OAc (2), OH (3), OSO2Me (4), Br (5), and N3 (6)) useful as precursors of new tripodal ligands have been prepared. Alkylation of initial tris(2‐hydroxyphenyl)phosphine oxide (1) resulted in triacetate 2, which was deprotected to triol 3. The latter has been converted into trimesylate 4, which has been treated with LiBr or NaN3 to give the corresponding tribromo or triazido derivatives 5 and 6, respectively. According to X‐ray diffraction, the molecules of compounds 2, 5, and 6 in crystal adopt conformation where two side arms are oriented to the same direction as the P=O group, while the third side arm is oriented in the opposite manner.

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“…Tertiary phosphine oxides (TPOs) are a very broad class of compounds used primarily as ligands in complexes with both late 1 and early 2 transition metals, but also in the coordination chemistry of f-block elements: many examples of complexes are known for lanthanides, 3,4 and a few for actinides, 5 and several possess valuable physical properties. 6 Strong binding with harder cations of sand f-block elements has led to their use as extractants 7,8 and also in several catalytic transformations. 1,9,10 There are many studies [11][12][13][14][15][16][17][18][19][20][21][22] of triaryl TPOs where all three groups are derivatives of benzene but the number of studies is dramatically decreased when one of the aryl groups is changed to heteroaryl.…”

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confidence: 99%

Palladium-Catalyzed C–P Cross-Coupling between (Het)aryl Halides and Secondary Phosphine Oxides

Zakirova¹,

Mladentsev²,

Borisova

2019

Synthesis

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An efficient procedure for C–P bond formation via the palladium-catalyzed [Pd(OAc)2/dppf/Cs2CO3] reaction between dichloroheterocycles and secondary phosphine oxides was developed. The steric and electronic properties of substituents were varied to establish the scope and limitations of the method developed. By applying these conditions, a variety of new heterocyclic compounds bearing two tertiary phosphine oxides were successfully synthesized in moderate to excellent yields. After adjustments to the reaction conditions [Pd(OAc)2/dippf/t-BuOK], cross-coupling of secondary phosphine oxides with bulky (secondary or tertiary alkyl) substituents on the phosphorus atom was achieved. Extension of the methodology to monohalohetarenes and monohaloarenes was successfully carried out; once again, the steric and electronic properties of the halides were varied widely. The desired reaction occurred in all cases studied, giving high to excellent yields of product regardless of the nature and positions of substituents.

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Coordination and extraction of lanthanides(III) with tripodal ligands on the triphenylphosphine oxide platform: Effect of uncoordinating substituents

Cited by 28 publications

References 45 publications

SYNTHESIS AND SPECTRAL PROPERTIES OF LANTANIDE COMPLEXES WITH A NEW TRIPODAL TRIS-CHELATING CAPh LIGAND

SYNTHESIS AND SPECTRAL PROPERTIES OF LANTANIDE COMPLEXES WITH A NEW TRIPODAL TRIS-CHELATING CAPh LIGAND

Synthesis and molecular structure of functionalized tris[2‐(4′‐substituted butoxyphenyl)]phosphine oxides as precursors of tripodal ligands

Palladium-Catalyzed C–P Cross-Coupling between (Het)aryl Halides and Secondary Phosphine Oxides

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