Dinuclear lanthanide(<scp>iii</scp>)/zinc(<scp>ii</scp>) complexes with methyl 2-pyridyl ketone oxime

Anastasiadis, Nikolaos C.; Polyzou, Christina D.; Kostakis, George E.; Bekiari, Vlasoula; Lan, Yanhua; Perlepes, Spyros P.; Konidaris, Konstantis F.; Powell, Annie K.

doi:10.1039/c5dt03663a

Cited by 21 publications

(9 citation statements)

References 35 publications

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“…The spectroscopic studies and the structures of the prepared complexes emphasize the importance of the information emerging from synthetic investigations that otherwise would not have been revealed through exclusively solution studies, while simultaneously shedding light onto the connection of the requisite chemistry with the removal of toxic Cd(II) using pyridyl oxime extractants [ 19 ]. The present work can be considered as a continuation of our intense interest in the coordination chemistry of pyridyl aldo/ketoximes and dioximes, and amidoximes/amidodioximes [ 14 , 27 , 29 , 30 , 31 , 32 , 33 , 34 , 35 , 36 , 37 , 38 , 39 , 40 ] and on various aspects of Cd(II) chemistry [ 14 , 40 , 41 , 42 , 43 , 44 , 45 ].…”

Section: Introductionmentioning

confidence: 99%

Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants

et al. 2022

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The present work describes the reactions of CdI2 with 2-pyridyl aldoxime (2paoH), 3-pyridyl aldoxime (3paoH), 4-pyridyl aldoxime (4paoH), 2-6-diacetylpyridine dioxime (dapdoH2) and 2,6-pyridyl diamidoxime (LH4). The primary goal was to contribute to understanding the molecular basis of the very good liquid extraction ability of 2-pyridyl ketoximes with long aliphatic chains towards toxic Cd(II) and the inability of their 4-pyridyl isomers for this extraction. Our systematic investigation provided access to coordination complexes [CdI2(2paoH)2] (1), {[CdI2(3paoH)2]}n (2), {[CdI2(4paoH)2]}n (3) and [CdI2(dapdoH2)] (4). The reaction of CdI2 and LH4 in EtOH resulted in a Cd(II)-involving reaction of the bis(amidoxime) and isolation of [CdI2(L’H2)] (5), where L’H2 is the new ligand 2,6-bis(ethoxy)pyridine diimine. A mechanism of this transformation has been proposed. The structures of 1, 2, 3, 4.2EtOH and 5 were determined by single-crystal X-ray crystallography. The complexes have been characterized by FT-IR and FT-Raman spectra in the solid state and the data are discussed in terms of structural features. The stability of the complexes in DMSO was investigated by 1H NMR spectroscopy. Our studies confirm that the excellent extraction ability of 2-pyridyl ketoximes is due to the chelating nature of the extractants leading to thermodynamically stable Cd(II) complexes. The monodentate coordination of 4-pyridyl ketoximes (as confirmed in our model complexes with 4paoH and 3paoH) seems to be responsible for their poor performance as extractants.

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Section: Introductionmentioning

confidence: 99%

Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants

et al. 2022

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“…This paper describes our results from the synthetic investigation of the general reaction system CdCl 2 ∙2H 2 O/phpaoH and from the full structural and spectroscopic characterization of the products; the implication of our study with respect to the solvent extraction of Cd(II) from aqueous chloride solutions by 2-pyridyl ketoximes have also been critically discussed. The present work can be considered as a continuation of our interest in several aspects of Cd(II) chemistry [15,16,17,18,19,20] and the coordination chemistry of 2-pyridyl oximes (aldo-, keto-, and amidoximes) [20,21,22,23,24,25,26,27,28,29,30,31,32,33]. Our previous experience on the latter area shows that phpaoH behaves similarly with methyl 2-pyridyl ketoxime (mepaoH; the substituent on the oxime carbon atom is a methyl group) [21,30] in 3d- and mixed 3d/4f-metal complexes, and this justifies partly the choice of phpaoH for our model studies.…”

Section: Introductionmentioning

confidence: 99%

Modeling the Solvent Extraction of Cadmium(II) from Aqueous Chloride Solutions by 2-pyridyl Ketoximes: A Coordination Chemistry Approach

et al. 2019

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The goal of this work is to model the nature of the chemical species [CdCl2(extractant)2] that are formed during the solvent (or liquid-liquid) extraction of the toxic cadmium(II) from chloride-containing aqueous media using hydrophobic 2-pyridyl ketoximes as extractants. Our coordination chemistry approach involves the study of the reactions between cadmium(II) chloride dihydrate and phenyl 2-pyridyl ketoxime (phpaoH) in water-containing acetone. The reactions have provided access to complexes [CdCl2(phpaoH)2]∙H2O (1∙H2O) and {[CdCl2(phpaoH)]}n (2); the solid-state structures of which have been determined by single-crystal X-ray crystallography. In both complexes, phpaoH behaves as an N,N’-bidentate chelating ligand. The complexes have been characterized by solid-state IR and Raman spectra, and by solution 1H NMR spectra. The preparation and characterization of 1∙H2O provide strong evidence for the existence of the species [CdCl2(extractant)2] that have been proposed to be formed during the liquid-liquid extraction process of Cd(II), allowing the efficient transfer of the toxic metal ion from the aqueous phase into the organic phase.

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“…[17]. Restricting further discussion to the former family of ligands, the emphasis of our efforts (only selected references from our work are given below) has been on (a) the optical and magnetic properties of the resulting homo-and heterometallic dinuclear [18][19][20][21] and polynuclear [22][23][24][25][26][27] complexes, (b) the metal-mediated/promoted/assisted reactivity of these ligands [28][29][30], and (c) the modeling of the solvent extraction of toxic metal ions from aqueous solutions by 2-pyridyl ketoximes [31,32]. A literature survey reveals that a plethora of homometallic complexes of paoH, mepaoH, phpaoH, and ClpaoH (Figure 1), in their neutral or anionic forms, have been prepared and studied with transition [22][23][24][25][27][28][29]31,32] and actinide [21] metal ions.…”

Section: Introductionmentioning

confidence: 99%

Dinuclear Lanthanide(III) Complexes from the Use of Methyl 2-Pyridyl Ketoxime: Synthetic, Structural, and Physical Studies

et al. 2021

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The first use of methyl 2-pyridyl ketoxime (mepaoH) in homometallic lanthanide(III) [Ln(III)] chemistry is described. The 1:2 reactions of Ln(NO3)3·nH2O (Ln = Nd, Eu, Gd, Tb, Dy; n = 5, 6) and mepaoH in MeCN have provided access to complexes [Ln2(O2CMe)4(NO3)2(mepaoH)2] (Ln = Nd, 1; Ln = Eu, 2; Ln = Gd, 3; Ln = Tb, 4; Ln = Dy, 5); the acetato ligands derive from the LnIII—mediated hydrolysis of MeCN. The 1:1 and 1:2 reactions between Dy(O2CMe)3·4H2O and mepaoH in MeOH/MeCN led to the all-acetato complex [Dy2(O2CMe)6(mepaoH)2] (6). Treatment of 6 with one equivalent of HNO3 gave 5. The structures of 1, 5, and 6 were solved by single-crystal X-ray crystallography. Elemental analyses and IR spectroscopy provide strong evidence that 2–4 display similar structural characteristics with 1 and 5. The structures of 1–5 consist of dinuclear molecules in which the two LnIII centers are bridged by two bidentate bridging (η1:η1:μ2) and two chelating-bridging (η1:η2:μ2) acetate groups. The LnIII atoms are each chelated by a N,N’-bidentate mepaoH ligand and a near-symmetrical bidentate nitrato group. The molecular structure of 6 is similar to that of 5, the main difference being the presence of two chelating acetato groups in the former instead of the two chelating nitrato groups in the latter. The geometry of the 9-coordinate LnIII centers in 1, 5 and 6 can be best described as a muffin-type (MFF-9). The 3D lattices of the isomorphous 1 and 5 are built through H-bonding, π⋯π stacking and C-H⋯π interactions, while the 3D architecture of 6 is stabilized by H bonds. The IR spectra of the complexes are discussed in terms of the coordination modes of the organic and inorganic ligands involved. The Eu(III) complex 2 displays a red, metal-ion centered emission in the solid state; the TbIII atom in solid 4 emits light in the same region with the ligand. Magnetic susceptibility studies in the 2.0–300 K range reveal weak antiferromagnetic intramolecular GdIII…GdIII exchange interactions in 3; the J value is −0.09(1) cm−1 based on the spin Hamiltonian Ĥ = −J(ŜGd1·ŜGd2).

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Dinuclear lanthanide(iii)/zinc(ii) complexes with methyl 2-pyridyl ketone oxime

Cited by 21 publications

References 35 publications

Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants

Confirming the Molecular Basis of the Solvent Extraction of Cadmium(II) Using 2-Pyridyl Oximes through a Synthetic Inorganic Chemistry Approach and a Proposal for More Efficient Extractants

Modeling the Solvent Extraction of Cadmium(II) from Aqueous Chloride Solutions by 2-pyridyl Ketoximes: A Coordination Chemistry Approach

Dinuclear Lanthanide(III) Complexes from the Use of Methyl 2-Pyridyl Ketoxime: Synthetic, Structural, and Physical Studies

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