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Metal Based Compounds with “Non-Innocent” Ligands: Structure, Property and Ligand-Driven Reactivity

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

Deadline for manuscript submissions: closed (31 March 2021) | Viewed by 21002

Special Issue Editor


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Guest Editor
G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, 49 Tropinina str, 603137 Nizhny Novgorod, Russia
Interests: redox active ligands; complex compounds; small molecules; electronic paramagnetic resonance; magnetic properties

Special Issue Information

Dear Colleagues,

In nature, enzymes in which active sites contain different metal centers are responsible for many important chemical transformations, which require the transfer of one or more electrons, and are involved in such important processes as oxidation, reduction, hydrolysis, etc. For example, the oxidation of water with Photosystem II, the reduction of O2 with cytochrome oxidase, or fixation of N2, the disproportionation of the superoxide anion radical into oxygen and hydrogen peroxide under the influence of the antioxidant enzyme superoxide dismutase, hydrolysis of phosphate acid esters with phosphatases, etc. Like biological active sites, the synthetic metal complexes used for similar chemical processes (for example, the oxidation of water or the reduction of molecular oxygen) also demonstrate the influence of the nature of the metal fragment on the complex reactivity. The great interest in many chemical processes, which are used in various fields from the catalytic synthetic processes to the capture and storage of solar energy, and are carried out with the involvement of metal-containing compounds, causes numerous attempts to mimic both the structure and function of these compounds. A great deal of attention is paid to the investigation of the interactions between metals, metal-containing organic fragments and organic ligands in synthetic metal complexes and how these interactions affect the electronic structure, redox active properties, electron transfer, and chemical reactivity of compounds. In many cases, not only the central metal atom (ion) participates directly in the chemical processes, but also its ligand environment. Ligands which participate directly in various transformations and have a significant effect on the molecular, electronic structure and reactivity of compounds are commonly called as “non-innocent” or redox-active ligands.

This Special Issue is dedicated to the latest achievements in the field of coordination, organometallic compounds, the structure and reactivity of which are largely determined not only and not so much by the metal, but also by ligands. The results of fundamental research (the synthesis, the investigation of molecular and electronic structure using spectroscopic methods, X-ray structural analysis, the study of chemical, redox, magnetic, biochemical, photochemical and optical properties, etc.) and applied research (the application in various reactions of fine organic/organoelemental synthesis, catalytic processes, the various aspects of compounds application in electro-, photo-, biochemistry, medicine, optics, electronics, etc.) are planned for the publication in this Special Issue. Full papers, communications, and reviews on these topics are welcome.

Prof. Dr. Andrey I. Poddel'sky
Guest Editor

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Keywords

  • metal complex
  • “non-innocent” ligand
  • synthesis
  • molecular and electronic structure
  • ligand-driven reactivity
  • application

Published Papers (6 papers)

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Research

14 pages, 2125 KiB  
Article
Generation of a Hetero Spin Complex from Iron(II) Iodide with Redox Active Acenaphthene-1,2-Diimine
by Dmitriy S. Yambulatov, Stanislav A. Nikolaevskii, Mikhail A. Kiskin, Kirill V. Kholin, Mikhail N. Khrizanforov, Yulia G. Budnikova, Konstantin A. Babeshkin, Nikolay N. Efimov, Alexander S. Goloveshkin, Vladimir K. Imshennik, Yurii V. Maksimov, Evgeny M. Kadilenko, Nina P. Gritsan and Igor L. Eremenko
Molecules 2021, 26(10), 2998; https://doi.org/10.3390/molecules26102998 - 18 May 2021
Cited by 11 | Viewed by 2921
Abstract
The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)FeIII2] (1). Molecular structure of 1 was determined by the single crystal X-ray diffraction analysis. The spin state of [...] Read more.
The reaction of the redox active 1,2-bis[(2,6-diisopropylphenyl)imino]acenaphthene (dpp-BIAN) and iron(II) iodide in acetonitrile led to a new complex [(dpp-BIAN)FeIII2] (1). Molecular structure of 1 was determined by the single crystal X-ray diffraction analysis. The spin state of the iron cation in complex 1 at room temperature and the magnetic behavior of 1 in the temperature range of 2–300 K were studied using Mossbauer spectroscopy and magnetic susceptibility measurements, respectively. The neutral character of dpp-BIAN in 1 was confirmed by IR and UV spectroscopy. The electrochemistry of 1 was studied in solution and solid state using cyclic voltammetry. The generation of the radical anion form of the dpp-BIAN ligand upon reduction of 1 in a CH2Cl2 solution was monitored by EPR spectroscopy. Full article
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17 pages, 1855 KiB  
Article
Triphenylantimony(V) Catecholates of the Type (3-RS-4,6-DBCat)SbPh3-Catechol Thioether Derivatives: Structure, Electrochemical Properties, and Antiradical Activity
by Ivan V. Smolyaninov, Georgy K. Fukin, Nadezhda T. Berberova and Andrey I. Poddel’sky
Molecules 2021, 26(8), 2171; https://doi.org/10.3390/molecules26082171 - 9 Apr 2021
Cited by 6 | Viewed by 1948
Abstract
A new series of triphenylantimony(V) 3-alkylthio/arylthio-substituted 4,6-di-tert-butylcatecholates of the type (3-RS-4,6-DBCat)SbPh3, where R = n-butyl (1), n-hexyl (2), n-octyl (3), cyclopentyl (4), cyclohexyl (5), benzyl (6), phenyl (7 [...] Read more.
A new series of triphenylantimony(V) 3-alkylthio/arylthio-substituted 4,6-di-tert-butylcatecholates of the type (3-RS-4,6-DBCat)SbPh3, where R = n-butyl (1), n-hexyl (2), n-octyl (3), cyclopentyl (4), cyclohexyl (5), benzyl (6), phenyl (7), and naphthyl-2 (8), were synthesized from the corresponding catechol thioethers and Ph3SbBr2 in the presence of a base. The crystal structures of 1, 2, 3, and 5 were determined by single-crystal X-ray analysis. The coordination polyhedron of 13 is better described as a tetragonal pyramid with a different degree of distortion, while that for 5- was a distorted trigonal bipyramid (τ = 0.014, 0.177, 0.26, 0.56, respectively). Complexes demonstrated different crystal packing of molecules. The electrochemical oxidation of the complexes involved the catecholate group as well as the thioether linker. The introduction of a thioether fragment into the aromatic ring of catechol ligand led to a shift in the potential of the “catechol/o-semiquinone” redox transition to the anodic region, which indicated the electron-withdrawing nature of the RS group. The radical scavenging activity of the complexes was determined in the reaction with DPPH radical. Full article
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17 pages, 2991 KiB  
Article
Series of Near-IR-Absorbing Transition Metal Complexes with Redox Active Ligands
by Esko Salojärvi, Anssi Peuronen, Manu Lahtinen, Hannu Huhtinen, Leonid S. Vlasenko, Mika Lastusaari and Ari Lehtonen
Molecules 2020, 25(11), 2531; https://doi.org/10.3390/molecules25112531 - 29 May 2020
Cited by 11 | Viewed by 3933
Abstract
New soluble and intensely near-IR-absorbing transition metal (Ti, Zr, V, Ni) complexes were synthesized using a redox non-innocent N,N’-bis(3,5-di-tertbutyl-2-hydroxy-phenyl) -1,2-phenylenediamine (H4L) as a ligand precursor. In all the complexes, ([Ti(Lox)2, [Zr(Lox)2 [...] Read more.
New soluble and intensely near-IR-absorbing transition metal (Ti, Zr, V, Ni) complexes were synthesized using a redox non-innocent N,N’-bis(3,5-di-tertbutyl-2-hydroxy-phenyl) -1,2-phenylenediamine (H4L) as a ligand precursor. In all the complexes, ([Ti(Lox)2, [Zr(Lox)2], [V(Lsq1)(HLox)] and [Ni(HLox)2], two organic molecules coordinate to the metal center as tri- or tetradentate ligands. The solid-state structures of the complexes were determined using single crystal XRD, and the compounds were further characterized with Electrospray Ionisation Mass Spectrometry (ESI-MS). Thermoanalytical measurements indicated the thermal stabilities of the complexes. All compounds absorb strongly in the near-IR region and show very interesting magnetic and electrochemical properties. Moreover, it was shown that the V and Ni complexes can also convert absorbed near-IR photons to (un)paired electrons, which indicates great promise in photovoltaic applications. Full article
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16 pages, 2304 KiB  
Article
Complexes of Cobalt(II) Iodide with Pyridine and Redox Active 1,2-Bis(arylimino)acenaphthene: Synthesis, Structure, Electrochemical, and Single Ion Magnet Properties
by Dmitriy S. Yambulatov, Stanislav A. Nikolaevskii, Mikhail A. Kiskin, Tatiana V. Magdesieva, Oleg A. Levitskiy, Denis V. Korchagin, Nikolay N. Efimov, Pavel N. Vasil’ev, Alexander S. Goloveshkin, Alexey A. Sidorov and Igor L. Eremenko
Molecules 2020, 25(9), 2054; https://doi.org/10.3390/molecules25092054 - 28 Apr 2020
Cited by 27 | Viewed by 5283
Abstract
Complexes [(dpp-BIAN)0CoIII2]·MeCN (I) and [(Py)2CoI2] (II) were synthesized by the reaction between cobalt(II) iodide and 1,2-bis(2,6-diisopropylphenylimino)acenaphthene (dpp-BIAN) or pyridine (Py), respectively. The molecular structures of the complexes were determined [...] Read more.
Complexes [(dpp-BIAN)0CoIII2]·MeCN (I) and [(Py)2CoI2] (II) were synthesized by the reaction between cobalt(II) iodide and 1,2-bis(2,6-diisopropylphenylimino)acenaphthene (dpp-BIAN) or pyridine (Py), respectively. The molecular structures of the complexes were determined by X-ray diffraction. The Co(II) ions in both compounds are in a distorted tetrahedral environment (CoN2I2). The electrochemical behavior of complex I was studied by cyclic voltammetry. Magnetochemical measurements revealed that when an external magnetic field is applied, both compounds exhibit the properties of field-induced single ion magnets. Full article
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13 pages, 1185 KiB  
Article
Easy Ligand Activation in the Coordination Sphere of Ru inside the [PW11O39]7– Backbone
by Anna A. Mukhacheva, Artem L. Gushchin, Vadim V. Yanshole, Pavel A. Abramov and Maksim N. Sokolov
Molecules 2020, 25(8), 1859; https://doi.org/10.3390/molecules25081859 - 17 Apr 2020
Cited by 4 | Viewed by 2730
Abstract
Irradiation of the Keggin-type [PW11O39{Ru(NO)}]4− (Ru-NO) polyoxometalate in CH3CN results in rapid NO ligand elimination with the formation of [PW11O39{RuIII(CH3CN)}]4− (Ru-CH3CN). [...] Read more.
Irradiation of the Keggin-type [PW11O39{Ru(NO)}]4− (Ru-NO) polyoxometalate in CH3CN results in rapid NO ligand elimination with the formation of [PW11O39{RuIII(CH3CN)}]4− (Ru-CH3CN). This complex offers an easy entry into the Ru-based chemistry of the {PW11Ru} complex. Attempts to substitute N3 for CH3CN in the presence of an NaN3 excess lead a variety of products: (i) [PW11O39{RuIII(N3)}]4− (Ru-N3); (ii) [PW11O39{RuIII(N4HC-CH3)}]4− (Ru-Tz) as a click-reaction product; and (iii) [PW11O39{RuII(N2)}]5− (Ru-N2). UV-VIS, CV, and HR-ESI-MS techniques were used for the reaction monitoring and characterization of the products. Full article
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23 pages, 5609 KiB  
Article
Polyfunctional Sterically Hindered Catechols with Additional Phenolic Group and Their Triphenylantimony(V) Catecholates: Synthesis, Structure, and Redox Properties
by Ivan V. Smolyaninov, Andrey I. Poddel’sky, Susanna A. Smolyaninova, Maxim V. Arsenyev, Georgy K. Fukin and Nadezhda T. Berberova
Molecules 2020, 25(8), 1770; https://doi.org/10.3390/molecules25081770 - 12 Apr 2020
Cited by 10 | Viewed by 3136
Abstract
New polyfunctional sterically hindered 3,5-di-tert-butylcatechols with an additional phenolic group in the sixth position connected by a bridging sulfur atom—(6-(CH2-S-tBu2Phenol)-3,5-DBCat)H2 (L1), (6-(S-tBu2Phenol)-3,5-DBCat)H2 (L2), and (6-(S-Phenol)-3,5-DBCat)H2 ( [...] Read more.
New polyfunctional sterically hindered 3,5-di-tert-butylcatechols with an additional phenolic group in the sixth position connected by a bridging sulfur atom—(6-(CH2-S-tBu2Phenol)-3,5-DBCat)H2 (L1), (6-(S-tBu2Phenol)-3,5-DBCat)H2 (L2), and (6-(S-Phenol)-3,5-DBCat)H2 (L3) (3,5-DBCat is dianion 3,5-di-tert-butylcatecolate)—were synthesized and characterized in detail. The exchange reaction between catechols L1 and L3 with triphenylantimony(V) dibromide in the presence of triethylamine leads to the corresponding triphenylantimony(V) catecholates (6-(CH2-S-tBu2Phenol)-3,5-DBCat)SbPh3 (1) and (6-(S-Phenol)-3,5-DBCat)SbPh3 (2). The electrochemical properties of catechols L1L3 and catecholates 1 and 2 were investigated using cyclic voltammetry. The electrochemical oxidation of L1L3 at the first stage proceeds with the formation of the corresponding o-benzoquinones. The second process is the oxidation of the phenolic moiety. Complexes 1 and 2 significantly expand their redox capabilities, owing to the fact that they can act as the electron donors due to the catecholate metallocycle capable of sequential oxidations, and as donors of the hydrogen atoms, thus forming a stable phenoxyl radical. The molecular structures of the free ligand L1 and complex 1 in the crystal state were determined by single-crystal X-ray analysis. Full article
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