Iron(III) complexes with 2-pyridyl oxime ligands: Synthesis, structural and spectroscopic characterization, and magnetic studies

Tzani, Sofia; Lazarou, Katerina N.; Stoumpos, Constantinos C.; Pissas, M.; Psycharis, Vassilis; Sanakis, Yiannis; Raptopoulou, Catherine P.

doi:10.1002/slct.201600037

Cited by 7 publications

(3 citation statements)

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“…For MeCN, the two hydrolysis steps are illustrated in Figure 2 . Several metal ion-mediated processes for the hydration of nitriles with selective formation of metal-bound carboxamides are known [ 27 , 51 , 52 , 53 ], but most of the systems are not catalytic and only a few of them are able to hydrate R’-C≡N under homogeneous catalytic conditions [ 13 , 53 ], usually exhibiting a low activity [ 53 ]. The second step of the metal-ion mediated hydrolysis, i.e., conversion to carboxylic acids and ammonia, has been observed only in few cases involving Pt(IV), Os(IV), and Nb(V) systems [ 53 ].…”

Section: Resultsmentioning

confidence: 99%

“…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. In contrast, with the exception of [LnCl 3 (phpaoH) 3 ] (Ln = Nd [ 33 ], Sm [ 34 ]), such complexes are not known in lanthanide (Ln) chemistry.…”

Section: Introductionmentioning

confidence: 99%

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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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Section: Resultsmentioning

confidence: 99%

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 iron(III) pyridylimine complex was obtained as the dark green crystalline with about 50 % yield. The complex was characterized with FTIR and high-resolution MS. FTIR absorption peaks (KBr, pellets): 1348 cm À 1 (pyridyl C=N stretching, very strong), [25] 1600-1650 cm À 1 (aromatic C=C stretching, weak), 3404 cm À 1 (OÀ H stretching from H 2 O, broad and strong); HRMS for [C 30 H 22 N 6 Fe] + m/z: calc. 522.1256, found 522.1253.…”

Section: Methodsmentioning

confidence: 99%

Synthesis of Pyridyl‐Imine Complex of Iron(III) as a Fluorescent Sensor for Hydrazine Detection Based on Redox Chemistry

Zhang

Tam

et al. 2022

ChemistrySelect

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A six-coordinated iron(III) pyridyl-imine complex was synthesized by one-pot reaction and was demonstrated as a fluorescent sensor for the detection of hydrazine in solution based on the redox reaction. The fluorescence signal generated was attributed to the reduction of the oxidative iron-center of Fe(III) to Fe(II) by the reductive hydrazine. A good linear relationship for the analysis of hydrazine was obtained with the concentration range of 0.06-0.15 mM (R 2 = 0.99114) in DMF solution. The limit of detection (LOD) estimated was 14.8 μM and the limit of quantitation (LOQ) was 49 μM. Moreover, the color change of the iron(III) pyridyl-imine complex solution from dark green to reddish brown was able to observed by naked eye, indicating that the Fe(III)-complex may be also utilized as a colorimetric sensor for hydrazine at millimolar level. The present study demonstrated an interesting fluorescent sensing system based on redox chemistry of an iron(III) complex that generated fluorescence response upon reacting with its redox pair such as the reducing agent hydrazine.

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Inverse coordination – An emerging new chemical concept. Oxygen and other chalcogens as coordination centers

Haiduc

2017

Coordination Chemistry Reviews

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Iron(III) complexes with 2-pyridyl oxime ligands: Synthesis, structural and spectroscopic characterization, and magnetic studies

Cited by 7 publications

References 52 publications

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

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

Synthesis of Pyridyl‐Imine Complex of Iron(III) as a Fluorescent Sensor for Hydrazine Detection Based on Redox Chemistry

Inverse coordination – An emerging new chemical concept. Oxygen and other chalcogens as coordination centers

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