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Synthesis and Reactivity of Transition Metal Complexes

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Organometallic Chemistry".

Deadline for manuscript submissions: closed (1 June 2023) | Viewed by 6133

Special Issue Editor


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Guest Editor
Nikolaev Institute of Inorganic Chemistry SB RAS, 630090 Novosibirsk, Russia
Interests: coordination chemistry; transition metals; redox active ligands; noble metals; synthesis; reactivity; catalytic applications
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

The coordination chemistry of transition metals is one of the most important and extensive areas of modern chemistry. It is closely related to other fields such as supramolecular chemistry, photochemistry, catalysis, medicine, materials science, quantum chemistry, etc.

This Special Issue is devoted to all aspects of transition metal chemistry, including the synthesis and characterization of new complexes and materials, the features of the molecular and electronic structure of complexes, the study of their reactivity and catalytic properties, the design of new supramolecular assemblies based on them, and the use of metal complexes in photochemistry, bioinorganic chemistry, medicine, etc.

Dr. Artem L. Gushchin
Guest Editor

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Keywords

  • transition metals
  • complexes; synthesis
  • crystal structure
  • ligands
  • reactivity
  • catalysis
  • applications

Published Papers (4 papers)

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Research

10 pages, 2568 KiB  
Article
Structure Determination of Binuclear Triple-Decker Phthalocyaninato Complexes by NMR via Paramagnetic Shifts Analysis Using Symmetry Peculiarities
by Sergey P. Babailov, Eugeny N. Zapolotsky, Eduard S. Fomin, Marina A. Polovkova, Gayane A. Kirakosyan, Alexander G. Martynov and Yulia G. Gorbunova
Molecules 2022, 27(22), 7836; https://doi.org/10.3390/molecules27227836 - 14 Nov 2022
Cited by 1 | Viewed by 1041
Abstract
The detailed knowledge about the structure of multinuclear paramagnetic lanthanide complexes for the targeted design of these compounds with special magnetic, sensory, optical and electronic properties is a very important task. At the same time, establishing the structure of such multinuclear paramagnetic lanthanide [...] Read more.
The detailed knowledge about the structure of multinuclear paramagnetic lanthanide complexes for the targeted design of these compounds with special magnetic, sensory, optical and electronic properties is a very important task. At the same time, establishing the structure of such multinuclear paramagnetic lanthanide complexes in solution, using NMR is a difficult task, since several paramagnetic centers act simultaneously on the resulting chemical shift of a particular nucleus. In this paper, we have demonstrated the possibility of molecular structure determination in solution on the example of binuclear triple-decker lanthanide(III) complexes with tetra-15-crown-5-phthalocyanine Ln2[(15C5)4Pc]3 {where Ln = Tb (1) and Dy (2)} by quantitative analysis of the pseudo-contact lanthanide-induced shifts (LIS). The symmetry of complexes was used for the simplification of the calculation of pseudo-contact shifts on the base of the expression for the magnetic susceptibility tensor in the arbitrary oriented magnetic axis system. Good agreement between the calculated and experimental shifts in the 1H NMR spectra indicates the similarity of the structure for the complexes 1 and 2 in solution of CDCl3 and the structure in the crystalline phase, found from the data of the X-ray structural study of the similar complex Lu2[(15C5)4Pc]3. The described approach can be useful for LIS analysis of other polynuclear symmetric lanthanide complexes. Full article
(This article belongs to the Special Issue Synthesis and Reactivity of Transition Metal Complexes)
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8 pages, 2065 KiB  
Communication
Holmium Complex with Phospholipids as 1H NMR Relaxational Sensor of Temperature and Viscosity
by Olga Yu. Selyutina and Sergei P. Babailov
Molecules 2022, 27(19), 6691; https://doi.org/10.3390/molecules27196691 - 08 Oct 2022
Cited by 2 | Viewed by 1125
Abstract
The sensitivity of Ho–phospholipid complexes to changes in the membrane viscosity of liposomes was checked. An increase in viscosity was observed for DPPC and DMPC near the phase-transition temperature. Ho–phospholipid complexes could be used as sensors of local membrane viscosity in NMR and [...] Read more.
The sensitivity of Ho–phospholipid complexes to changes in the membrane viscosity of liposomes was checked. An increase in viscosity was observed for DPPC and DMPC near the phase-transition temperature. Ho–phospholipid complexes could be used as sensors of local membrane viscosity in NMR and MRI technologies. Full article
(This article belongs to the Special Issue Synthesis and Reactivity of Transition Metal Complexes)
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9 pages, 2612 KiB  
Article
Paramagnetic Properties and Moderately RapidConformational Dynamics in the Cobalt(II) Calix[4]arene Complex by NMR
by Eugeny Nikolaevich Zapolotsky, Sergey Pavlovich Babailov and Gennadiy Alexandrovich Kostin
Molecules 2022, 27(14), 4668; https://doi.org/10.3390/molecules27144668 - 21 Jul 2022
Cited by 1 | Viewed by 1515
Abstract
1H NMR measurements are reported for the CD2Cl2/CDCl3 solutions of the Co(II) calix[4]arenetetraphosphineoxide complex (I). Temperature dependences of the 1H NMR spectra of I have been analyzed using the line shape analysis, taking into [...] Read more.
1H NMR measurements are reported for the CD2Cl2/CDCl3 solutions of the Co(II) calix[4]arenetetraphosphineoxide complex (I). Temperature dependences of the 1H NMR spectra of I have been analyzed using the line shape analysis, taking into account the temperature variation of paramagnetic chemical shifts, within the frame of the dynamic NMR method. Conformational dynamics of the 2:1 Co(II) calix[4]arene complexes was conditioned by the pinched conepinched cone interconversion of I (with activation Gibbs energy ΔG(298K) = 40 ± 3 kJ/mol. Due to substantial temperature dependence of paramagnetic shifts, complex I can be used as model compound for designing an NMR thermosensor reagent for local temperature monitoring. Full article
(This article belongs to the Special Issue Synthesis and Reactivity of Transition Metal Complexes)
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21 pages, 2954 KiB  
Article
Novel Copper(II) Complexes with Dipinodiazafluorene Ligands: Synthesis, Structure, Magnetic and Catalytic Properties
by Iakov S. Fomenko, Medhanie Afewerki, Marko I. Gongola, Eugene S. Vasilyev, Lidia S. Shul’pina, Nikolay S. Ikonnikov, Georgiy B. Shul’pin, Denis G. Samsonenko, Vadim V. Yanshole, Vladimir A. Nadolinny, Alexander N. Lavrov, Alexey V. Tkachev and Artem L. Gushchin
Molecules 2022, 27(13), 4072; https://doi.org/10.3390/molecules27134072 - 24 Jun 2022
Cited by 6 | Viewed by 1846
Abstract
The reactions of CuX2 (X = Cl, Br) with dipinodiazafluorenes yielded four new complexes [CuX2L1]2 (X = Cl (1), Br (2), L1 = (1R,3R,8R,10R)-2,2,9,9-Tetramethyl-3,4,7,8,9,10-hexahydro-1H-1,3:8,10-dimethanocyclopenta [1,2-b:5,4-b’]diquinolin-12(2H)-one) and [(CuX2)2L2 [...] Read more.
The reactions of CuX2 (X = Cl, Br) with dipinodiazafluorenes yielded four new complexes [CuX2L1]2 (X = Cl (1), Br (2), L1 = (1R,3R,8R,10R)-2,2,9,9-Tetramethyl-3,4,7,8,9,10-hexahydro-1H-1,3:8,10-dimethanocyclopenta [1,2-b:5,4-b’]diquinolin-12(2H)-one) and [(CuX2)2L2]n (X = Cl (3), Br (4), L2 = (1R,3R,8R,10R,1’R,3’R,8’R,10’R)-2,2,2’,2’,9,9,9’,9’-Octamethyl-1,1’,2,2’,3,3’,4,4’,7,7’,8,8’,9,9’,10,10’-hexadecahydro-1,3:1’,3’:8,10:8’,10’-tetramethano-12,12’-bi(cyclopenta [1,2-b:5,4-b’]diquinolinylidene). The complexes were characterized by IR and EPR spectroscopy, HR-ESI-MS and elemental analysis. The crystal structures of compounds 1, 2 and 4 were determined by X-ray diffraction (XRD) analysis. Complexes 12 have a monomeric structure, while complex 4 has a polymeric structure due to additional coordinating N,N sites in L2. All complexes contain a binuclear fragment {Cu2(μ-X)2×2} (X = Cl, Br) in their structures. Each copper atom has a distorted square-pyramidal coordination environment formed by two nitrogen atoms and three halogen atoms. The Cu-Nax distance is elongated compared to Cu-Neq. The EPR spectra of compounds 14 in CH3CN confirm their paramagnetic nature due to the d9 electronic configuration of the copper(II) ion. The magnetic properties of all compounds were studied by the method of static magnetic susceptibility. For complexes 1 and 2, the effective magnetic moments are µeff ≈ 1.87 and 1.83 µB (per each Cu2+ ion), respectively, in the temperature range 50–300 K, which are close to the theoretical spin value (1.73 µB). Ferromagnetic exchange interactions between Cu(II) ions inside {Cu2(μ-X)2X2} (X = Cl, Br) dimers (J/kB ≈ 25 and 31 K for 1 and 2, respectively) or between dimers (θ′ ≈ 0.30 and 0.47 K for 1 and 2, respectively) were found at low temperatures. For compounds 3 and 4, the magnetic susceptibility is well described by the Curie–Weiss law in the temperature range 1.77–300 K with µeff ≈ 1.72 and 1.70 µB for 3 and 4, respectively, and weak antiferromagnetic interactions ≈ −0.4 K for 3 and −0.65 K for 4). Complexes 14 exhibit high catalytic activity in the oxidation of alkanes and alcohols with peroxides. The maximum yield of cyclohexane oxidation products reached 50% (complex 3). Based on the data on the study of regio- and bond-selectivity, it was concluded that hydroxyl radicals play a decisive role in the oxidation reaction. The initial products in reactions with alkanes are alkyl hydroperoxides. Full article
(This article belongs to the Special Issue Synthesis and Reactivity of Transition Metal Complexes)
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