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Advances in Coordination Chemistry

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

Deadline for manuscript submissions: closed (31 May 2020) | Viewed by 49838

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Guest Editor
Department of Chemistry and Chemical Technology, University of Ljubljana, 1000 Ljubljana, Slovenia
Interests: coordination chemistry of molybdenum; polyoxomolybdates; coordination chemistry of zinc; metal complexes in catalysis; crystal structure; vibrational spectroscopy

Special Issue Information

Dear Colleagues,

The use of coordination compounds dates back to prehistoric times. The earliest documented use is probably that of alizarin, hydroxyanthraquinone, a textile dye that produces a bright red colour in combination with aluminium ions [Kaufmann, G.B. Coordination Chemistry: History. In Encyclopedia of Inorganic Chemistry; Scott, R.A., Ed.; Wiley: New York; USA, 2006]. A milestone in the evolution of coordination chemistry is the revolutionary theory by Alfred Werner in 1893, which laid foundations to modern coordination chemistry. Today, IUPAC defines a coordination compound as any compound that is composed of a central atom, usually that of a metal, to which is attached a surrounding array of other atoms or groups of atoms, each of which is called a ligand [IUPAC Recommendations 2005]. Active sites in many enzymes that regulate biological processes are coordination compounds, as well as many catalysts used in the transformation of organic substances. Studies of interactions between metal ions and ligands may provide insight into catalysed reactions. The field of coordination chemistry is wide, with almost each metal ion or ligand making up its own subfield. The abundant reports in recent literature show that interest in coordination chemistry remains unwaning and that focus has shifted from comprehensive theories of bonding towards the application and synthesis of compounds designed for specific use. We will dedicate this Special Issue to all aspects of coordination chemistry.

Dr. Barbara Modec
Guest Editor

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Keywords

  • synthesis of novel coordination compounds
  • synthesis of coordination compounds with tailor-made ligands for specific application
  • synthesis of coordination compounds with multitopic ligands
  • isomerism
  • solid state structures and intermolecular interactions
  • coordination compounds with extended structures or metal organic frameworks
  • spectroscopic properties
  • magnetic properties
  • coordination compounds as model compounds
  • coordination compounds as catalysts

Published Papers (13 papers)

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Research

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15 pages, 3125 KiB  
Article
Quasi-Isostructural Co(II) and Ni(II) Complexes with Mefenamato Ligand: Synthesis, Characterization, and Biological Activity
by Michał Gacki, Karolina Kafarska, Anna Pietrzak, Izabela Korona-Głowniak and Wojciech M. Wolf
Molecules 2020, 25(13), 3099; https://doi.org/10.3390/molecules25133099 - 7 Jul 2020
Cited by 12 | Viewed by 2861
Abstract
Three metal complexes of mefenamato ligand 1 were synthesized: [Co2(mef)4(EtOH)2(H2O)4]: 2; [Co(mef)2(MeOH)4]∙2MeOH: 3; and [Ni(mef)2(MeOH)4]∙2MeOH: 4. Their compositions and properties were investigated [...] Read more.
Three metal complexes of mefenamato ligand 1 were synthesized: [Co2(mef)4(EtOH)2(H2O)4]: 2; [Co(mef)2(MeOH)4]∙2MeOH: 3; and [Ni(mef)2(MeOH)4]∙2MeOH: 4. Their compositions and properties were investigated by elemental analysis (EA), flame atomic absorption spectrometry (FAAS), Fourier-transform infrared spectroscopy (FTIR), and thermogravimetric analysis (TGA). Crystal structures were determined by the single crystal X-ray diffraction technique. Additionally, their antioxidant and antimicrobial activity were established, thus proving good/moderate bioactivity against Gram-positive bacteria and yeasts. In the crystal structure of 2, an apical water molecule is shared between two adjacent cobalt(II) ions, resulting in the formation of a polymeric chain extending along the [100] direction. Meanwhile, structures 3 and 4 have strong intermolecular hydrogen bonds with diverse topologies that yield unique quasi-isostructural arrangements. The packing topology is reflected by the Hirshfeld surface analysis of intermolecular contacts. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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15 pages, 5351 KiB  
Article
Positional Isomerism in the N^N Ligand: How Much Difference Does a Methyl Group Make in [Cu(P^P)(N^N)]+ Complexes?
by Fabian Brunner, Alessandro Prescimone, Edwin C. Constable and Catherine E. Housecroft
Molecules 2020, 25(12), 2760; https://doi.org/10.3390/molecules25122760 - 15 Jun 2020
Cited by 9 | Viewed by 1994
Abstract
The synthesis and structural characterization of 5,6′-dimethyl-2,2′-bipyridine (5,6′-Me2bpy) are reported, along with the preparations and characterizations of [Cu(POP)(5,6′-Me2bpy)][PF6] and [Cu(xantphos)(5,6′-Me2bpy)][PF6] (POP = bis(2-(diphenylphosphanyl)phenyl)ether, xantphos = 4,5-bis(diphenylphosphanyl)-9,9-dimethyl-9H-xanthene). Single-crystal X-ray structure determinations of [...] Read more.
The synthesis and structural characterization of 5,6′-dimethyl-2,2′-bipyridine (5,6′-Me2bpy) are reported, along with the preparations and characterizations of [Cu(POP)(5,6′-Me2bpy)][PF6] and [Cu(xantphos)(5,6′-Me2bpy)][PF6] (POP = bis(2-(diphenylphosphanyl)phenyl)ether, xantphos = 4,5-bis(diphenylphosphanyl)-9,9-dimethyl-9H-xanthene). Single-crystal X-ray structure determinations of [Cu(POP)(5,6′-Me2bpy)][PF6] and [Cu(xantphos)(5,6′-Me2bpy)][PF6] confirmed distorted tetrahedral copper(I) coordination environments with the 5-methylpyridine ring of 5,6′-Me2bpy directed towards the (C6H4)2O unit of POP or the xanthene unit of xantphos. In the xantphos case, this preference may be attributed to C–H…π interactions involving both the 6-CH unit and the 5-methyl substituent in the 5-methylpyridine ring and the arene rings of the xanthene unit. 1H NMR spectroscopic data indicate that this ligand orientation is also preferred in solution. In solution and the solid state, [Cu(POP)(5,6′-Me2bpy)][PF6] and [Cu(xantphos)(5,6′-Me2bpy)][PF6] are yellow emitters, and, for powdered samples, photoluminescence quantum yields (PLQYs) are 12 and 11%, respectively, and excited-state lifetimes are 5 and 6 μs, respectively. These values are lower than PLQY and τ values for [Cu(POP)(6,6′-Me2bpy)][PF6] and [Cu(xantphos)(6,6′-Me2bpy)][PF6], and the investigation points to the 6,6′-dimethyl substitution pattern in the bpy ligand being critical for enhancement of the PLQY. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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10 pages, 976 KiB  
Article
Structural Study of the Compounds Formed in the Reactions of FeCl3·6H2O with Ni(OH)2 in the Presence of Dithiolenes HSRSH (R = C6H2Cl2 or C6H4)
by Esther Delgado, Elisa Hernández, María Pérez, Josefina Perles and Félix Zamora
Molecules 2020, 25(9), 2240; https://doi.org/10.3390/molecules25092240 - 10 May 2020
Viewed by 2495
Abstract
In our attempts to prepare coordination polymers by reaction of FeCl3·6H2O and Ni(OH)2 in the presence of dithiolenes HSC6H2X2SH (X = Cl or H), several ion pairs of compounds containing the anionic [...] Read more.
In our attempts to prepare coordination polymers by reaction of FeCl3·6H2O and Ni(OH)2 in the presence of dithiolenes HSC6H2X2SH (X = Cl or H), several ion pairs of compounds containing the anionic entity [Ni(SC6H2X2S)2] were obtained instead. It was also found that other species without dithiolene ligands were formed in these reactions, giving rise to different ion pairs and a tetrametallic cluster. The careful isolation of the different types of crystalline solids allowed the characterization of all of the resulting compounds by single crystal X-ray diffraction (SCXRD). In order to establish the amount of nickel and iron present in the crystals, complementary total reflection X-ray fluorescence (TXRF) analyses were performed. The eight different structural types that were obtained are described and compared with related ones found in the literature. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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15 pages, 5169 KiB  
Article
Directing 2D-Coordination Networks: Combined Effects of a Conformationally Flexible 3,2′:6′,3″-Terpyridine and Chain Length Variation in 4′-(4-n-Alkyloxyphenyl) Substituents
by Dalila Rocco, Alessandro Prescimone, Edwin C. Constable and Catherine E. Housecroft
Molecules 2020, 25(7), 1663; https://doi.org/10.3390/molecules25071663 - 4 Apr 2020
Cited by 9 | Viewed by 2384
Abstract
The synthesis and characterization of 4′-(4-n-propoxyphenyl)-3,2′:6′,3″-terpyridine is described. Five 2D-coordination networks have been isolated by crystal growth at room temperature from reactions of Co(NCS)2 with 4′-(4-n-alkyloxyphenyl)-3,2′:6′,3″-terpyridines in which the n-alkyl group is ethyl, n-propyl, n-butyl, [...] Read more.
The synthesis and characterization of 4′-(4-n-propoxyphenyl)-3,2′:6′,3″-terpyridine is described. Five 2D-coordination networks have been isolated by crystal growth at room temperature from reactions of Co(NCS)2 with 4′-(4-n-alkyloxyphenyl)-3,2′:6′,3″-terpyridines in which the n-alkyl group is ethyl, n-propyl, n-butyl, n-pentyl and n-hexyl in ligands 26, respectively. The single-crystal structures of [{Co(2)2(NCS)2}.0.6CHCl3]n, [{Co(3)2(NCS)2}.4CHCl3.0.25H2O]n, [{Co(4)2(NCS)2}.4CHCl3]n, [Co2(5)4(NCS)4]n and [Co(6)2(NCS)2]n have been determined, and powder X-ray diffraction has demonstrated that the single-crystal structures are representative of the bulk materials. Each compound possesses a (4,4) net with Co centres as 4-connecting nodes. For the assemblies containing 2, 3 and 4, the (4,4) net comprises two geometrically different rhombuses, and the nets pack in an ABAB... arrangement with cone-like arrangements of n-alkyloxyphenyl groups being accommodated in a similar unit in an adjacent net. An increase in the n-alkyloxy chain length has two consequences: there is a change in the conformation of the 3,2′:6′,3″-tpy metal-binding domain, and the (4,4) net comprises identical rhombuses. Similarities and differences between the assemblies with ligands 26 and the previously reported [{Co(1)2(NCS)2}.3MeOH]n and [{Co(1)2(NCS)2}.2.2CHCl3]n in which 1 is 4′-(4-methoxyphenyl)-3,2′:6′,3″-terpyridine are discussed. The results demonstrate the effects of combining a variable chain length in the 4′-(4-n-alkyloxyphenyl) substituents of 3,2′:6′,3″-tpy and a conformationally flexible 3,2′:6′,3″-tpy metal-binding domain. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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24 pages, 5741 KiB  
Article
Beyond the Simple Copper(II) Coordination Chemistry with Quinaldinate and Secondary Amines
by Barbara Modec, Nina Podjed and Nina Lah
Molecules 2020, 25(7), 1573; https://doi.org/10.3390/molecules25071573 - 30 Mar 2020
Cited by 26 | Viewed by 6362
Abstract
Copper(II) acetate has reacted in methanol with quinaldinic acid (quinoline-2-carboxylic acid) to form [Cu(quin)2(CH3OH)]∙CH3OH (1) (quin = an anionic form of the acid) with quinaldinates bound in a bidentate chelating manner. In the air, [...] Read more.
Copper(II) acetate has reacted in methanol with quinaldinic acid (quinoline-2-carboxylic acid) to form [Cu(quin)2(CH3OH)]∙CH3OH (1) (quin = an anionic form of the acid) with quinaldinates bound in a bidentate chelating manner. In the air, complex 1 gives off methanol and binds water. The conversion was monitored by IR spectroscopy. The aqua complex has shown a facile substitution chemistry with alicyclic secondary amines, pyrrolidine (pyro), and morpholine (morph). trans-[Cu(quin)2(pyro)2] (2) and trans-[Cu(quin)2(morph)2] (4) were obtained in good yields. The morpholine system has produced a by-product, trans-[Cu(en)2(H2O)2](morphCOO)2 (5) (morphCOO = morphylcarbamate), a result of the copper(II) quinaldinate reaction with ethylenediamine (en), an inherent impurity in morpholine, and the amine reaction with carbon dioxide. (pyroH)[Cu(quin)2Cl] (3) forms on the recrystallization of [Cu(quin)2(pyro)2] from dichloromethane, confirming a reaction between amine and the solvent. Similarly, a homologous amine, piperidine (pipe), and dichloromethane produced (pipeH)[Cu(quin)2Cl] (11). The piperidine system has afforded both mono- and bis-amine complexes, [Cu(quin)2(pipe)] (6) and trans-[Cu(quin)2(pipe)2] (7). The latter also exists in solvated forms, [Cu(quin)2(pipe)2]∙CH3CN (8) and [Cu(quin)2(pipe)2]∙CH3CH2CN (9). Interestingly, only the piperidine system has experienced a reduction of copper(II). The involvement of amine in the reduction was undoubtedly confirmed by identification of a polycyclic piperidine compound 10, 6,13-di(piperidin-1-yl)dodecahydro-2H,6H-7,14-methanodipyrido[1,2-a:1′,2′-e][1,5]diazocine. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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14 pages, 2863 KiB  
Article
Binding Kinetics of Ruthenium Pyrithione Chemotherapeutic Candidates to Human Serum Proteins Studied by HPLC-ICP-MS
by Katarina Marković, Radmila Milačič, Stefan Marković, Jerneja Kladnik, Iztok Turel and Janez Ščančar
Molecules 2020, 25(7), 1512; https://doi.org/10.3390/molecules25071512 - 26 Mar 2020
Cited by 7 | Viewed by 2908
Abstract
The development of ruthenium-based complexes for cancer treatment requires a variety of pharmacological studies, one of them being a drug’s binding kinetics to serum proteins. In this work, speciation analysis was used to study kinetics of ruthenium-based drug candidates with human serum proteins. [...] Read more.
The development of ruthenium-based complexes for cancer treatment requires a variety of pharmacological studies, one of them being a drug’s binding kinetics to serum proteins. In this work, speciation analysis was used to study kinetics of ruthenium-based drug candidates with human serum proteins. Two ruthenium (Ru) complexes, namely [(η6-p-cymene)Ru(1-hydroxypyridine-2(1H)-thionato)Cl] (1) and [(η6-p-cymene)Ru(1-hydroxypyridine-2(1H)-thionato)pta]PF6 (2) (where pta = 1,3,5-triaza-7-phosphaadamantane), were selected. Before a kinetics study, their stability in relevant media was confirmed by nuclear magnetic resonance (NMR). Conjoint liquid chromatography (CLC) monolithic column, assembling convective interaction media (CIM) protein G and diethylamino (DEAE) disks, was used for separation of unbound Ru species from those bound to human serum transferrin (Tf), albumin (HSA) and immunoglobulins G (IgG). Eluted proteins were monitored by UV spectrometry (278 nm), while Ru species were quantified by post-column isotope dilution inductively coupled plasma mass spectrometry (ID-ICP-MS). Binding kinetics of chlorido (1) and pta complex (2) to serum proteins was followed from 5 min up to 48 h after incubation with human serum. Both Ru complexes interacted mainly with HSA. Complex (1) exhibited faster and more extensive interaction with HSA than complex (2). The equilibrium concentration for complex (1) was obtained 6 h after incubation, when about 70% of compound was bound to HSA, 5% was associated with IgG, whereas 25% remained unbound. In contrast, the rate of interaction of complex (2) with HSA was much slower and less extensive and the equilibrium concentration was obtained 24 h after incubation, when about 50% of complex (2) was bound to HSA and 50% remained unbound. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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12 pages, 2758 KiB  
Article
2-Methylimidazole Copper Iminodiacetates for the Adsorption of Oxygen and Catalytic Oxidation of Cyclohexane
by Xi Chen, Dong-Li An, Xin-Qi Zhan and Zhao-Hui Zhou
Molecules 2020, 25(6), 1286; https://doi.org/10.3390/molecules25061286 - 12 Mar 2020
Cited by 6 | Viewed by 4116
Abstract
The mixed-ligand copper(II) iminodiacetates [Cu(ida)(2-mim)(H2O)2]·H2O (1), [Cu(ida)(2-mim)2]·2H2O (2), [Cu(ida)(2-mim)(H2O)]n·4.5nH2O (3), and [Cu2(ida)2(2-mim)2]n·nH2 [...] Read more.
The mixed-ligand copper(II) iminodiacetates [Cu(ida)(2-mim)(H2O)2]·H2O (1), [Cu(ida)(2-mim)2]·2H2O (2), [Cu(ida)(2-mim)(H2O)]n·4.5nH2O (3), and [Cu2(ida)2(2-mim)2]n·nH2O (4) (H2ida = iminodiacetic acid, 2-mim = 2-methylimidazole) were obtained from neutral or alkaline solutions at different temperatures. The novel complex 4 contains very small holes with diameters of 2.9 Å, which can adsorb O2 selectively and reversibly between 1.89 to 29.90 bars, compared with the different gases of N2, H2, CO2, and CH4. This complex is stable up to 150 °C based on thermal analyses and XRD patterns. The four complexes show catalytic activities that facilitate the conversion of cyclohexane to cyclohexanol and cyclohexanone with hydrogen peroxide in a solution. The total conversion is 31% for 4. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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23 pages, 4447 KiB  
Article
Structural Diversity of Nickel and Manganese Chloride Complexes with Pyridin-2-One
by Saša Petriček
Molecules 2020, 25(4), 846; https://doi.org/10.3390/molecules25040846 - 14 Feb 2020
Cited by 3 | Viewed by 3579
Abstract
Reactions of NiCl2·6H2O and pyridin-2-one (C5H5NO = Hhp) afforded novel molecular complexes, i.e., mononuclear [NiCl2(Hhp)4] (1), dinuclear [NiCl2(Hhp)(H2O)2]2.2Hhp (3 [...] Read more.
Reactions of NiCl2·6H2O and pyridin-2-one (C5H5NO = Hhp) afforded novel molecular complexes, i.e., mononuclear [NiCl2(Hhp)4] (1), dinuclear [NiCl2(Hhp)(H2O)2]2.2Hhp (3) and [Ni2Cl4(Hhp)5]·2MeCN (4), and an ionic complex [Ni(Hhp)6]Cl2 (2). Single-crystal X-ray analyses revealed two modes of Hhp ligation in these complexes: a monodentate coordination of carbonyl oxygen in all of them and an additional µ2-oxygen bridging coordination in the dinuclear complex 4. Three bridging molecules of Hhp span two nickel(II) ions in 4 with a 2.9802 (5) Å separation of the metal ions. Complex 3 is a chlorido-bridged nickel dimer with a planar Ni2(µ-Cl)2 framework. Hydrogen bonds and parallel stacking arrangements of the Hhp molecules govern the connectivity patterns in the crystals, resulting in 1D structures in 1 and 5 or 2D in 3. A single manganese compound [MnCl2(Hhp)4] (5), isostructural to 1, was isolated under the similar conditions. This is in contrast to four nickel(II) chloride complexes with Hhp. Thermal analyses proved the stability of complexes 1 and 3 in argon up to 145 °C and 100 °C, respectively. The decomposition of 1 and 3 yielded nickel in argon and nickel(II) oxide in air at 800 °C. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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16 pages, 2319 KiB  
Article
Synthesis and Crystal Chemistry of Octahedral Rhodium(III) Chloroamines
by Kirill V. Yusenko, Aleksandr S. Sukhikh, Werner Kraus and Sergey A. Gromilov
Molecules 2020, 25(4), 768; https://doi.org/10.3390/molecules25040768 - 11 Feb 2020
Cited by 6 | Viewed by 3224
Abstract
Rhodium(III) octahedral complexes with amine and chloride ligands are the most common starting compounds for preparing catalytically active rhodium(I) and rhodium(III) species. Despite intensive study during the last 100 years, synthesis and crystal structures of rhodium(III) complexes were described only briefly. Some [RhCl [...] Read more.
Rhodium(III) octahedral complexes with amine and chloride ligands are the most common starting compounds for preparing catalytically active rhodium(I) and rhodium(III) species. Despite intensive study during the last 100 years, synthesis and crystal structures of rhodium(III) complexes were described only briefly. Some [RhClx(NH3)6-x] compounds are still unknown. In this study, available information about synthetic protocols and the crystal structures of possible [RhClx(NH3)6−x] octahedral species are summarized and critically analyzed. Unknown crystal structures of (NH4)2[Rh(NH3)Cl5], trans–[Rh(NH3)4Cl2]Cl⋅H2O, and cis–[Rh(NH3)4Cl2]Cl are reported based on high quality single crystal X-ray diffraction data. The crystal structure of [Rh(NH3)5Cl]Cl2 was redetermined. All available crystal structures with octahedral complexes [RhClx(NH3)6-x] were analyzed in terms of their packings and pseudo-translational sublattices. Pseudo-translation lattices suggest face-centered cubic and hexagonal closed-packed sub-cells, where Rh atoms occupy nearly ideal lattices. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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16 pages, 3204 KiB  
Article
A Versatile Approach to Access Trimetallic Complexes Based on Trisphosphinite Ligands
by Juan Miranda-Pizarro, Macarena G. Alférez, M. Dolores Fernández-Martínez, Eleuterio Álvarez, Celia Maya and Jesús Campos
Molecules 2020, 25(3), 593; https://doi.org/10.3390/molecules25030593 - 29 Jan 2020
Cited by 3 | Viewed by 2517
Abstract
A straightforward method for the preparation of trisphosphinite ligands in one step, using only commercially available reagents (1,1,1-tris(4-hydroxyphenyl)ethane and chlorophosphines) is described. We have made use of this approach to prepare a small family of four trisphosphinite ligands of formula [CH3C{(C [...] Read more.
A straightforward method for the preparation of trisphosphinite ligands in one step, using only commercially available reagents (1,1,1-tris(4-hydroxyphenyl)ethane and chlorophosphines) is described. We have made use of this approach to prepare a small family of four trisphosphinite ligands of formula [CH3C{(C6H4OR2)3], where R stands for Ph (1a), Xyl (1b, Xyl = 2,6-Me2-C6H3), iPr (1c), and Cy (1d). These polyfunctional phosphinites allowed us to investigate their coordination chemistry towards a range of late transition metal precursors. As such, we report here the isolation and full characterization of a number of Au(I), Ag(I), Cu(I), Ir(III), Rh(III) and Ru(II) homotrimetallic complexes, including the structural characterization by X-ray diffraction studies of six of these compounds. We have observed that the flexibility of these trisphosphinites enables a variety of conformations for the different trimetallic species. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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10 pages, 2501 KiB  
Article
A Pair of CoII Supramolecular Isomers Based on Flexible Bis-Pyridyl-Bis-Amide and Angular Dicarboxylate Ligands
by Pradhumna Mahat Chhetri, Ming-Hao Wu, Chou-Ting Hsieh, Xiang-Kai Yang, Chen-Ming Wu, En-Che Yang, Chih-Chieh Wang and Jhy-Der Chen
Molecules 2020, 25(1), 201; https://doi.org/10.3390/molecules25010201 - 3 Jan 2020
Cited by 2 | Viewed by 2325
Abstract
Thermal reactions of cobalt(II) salts with flexible N,N′-bis(pyrid-3-ylmethyl)adipoamide (L) and angular 4,4′-sulfonyldibenzoic acid (H2SDA) in H2O and CH3OH afforded a pair of supramolecular isomers: [Co2(L)(SDA)2], 1, and [...] Read more.
Thermal reactions of cobalt(II) salts with flexible N,N′-bis(pyrid-3-ylmethyl)adipoamide (L) and angular 4,4′-sulfonyldibenzoic acid (H2SDA) in H2O and CH3OH afforded a pair of supramolecular isomers: [Co2(L)(SDA)2], 1, and [Co2(L)(SDA)2]⋅CH3OH⋅H2O, 2. The structure of complex 1 can be simplified as a one-dimensional (1D) looped chain with L ligands penetrating into the middles of squares, forming a new type of self-catenated net with the (42⋅54)(4)2(5)2 topology, whereas complex 2 displays a 2-fold interpenetrated 2D net with the rare (42⋅68⋅8⋅104)(4)2-2,6L1 topology. While both complexes 1 and 2 display antiferromagnetism with strong spin-orbital coupling, the antiferromagnetism of 2 is accompanied by a cross-over behavior and probably a spin canting phenomenon. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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Review

Jump to: Research

58 pages, 11179 KiB  
Review
Recent Advances in the Chemistry of Metal Carbamates
by Giulio Bresciani, Lorenzo Biancalana, Guido Pampaloni and Fabio Marchetti
Molecules 2020, 25(16), 3603; https://doi.org/10.3390/molecules25163603 - 7 Aug 2020
Cited by 25 | Viewed by 6372
Abstract
Following a related review dating back to 2003, the present review discusses in detail the various synthetic, structural and reactivity aspects of metal species containing one or more carbamato ligands, representing a large family of compounds across all the periodic table. A preliminary [...] Read more.
Following a related review dating back to 2003, the present review discusses in detail the various synthetic, structural and reactivity aspects of metal species containing one or more carbamato ligands, representing a large family of compounds across all the periodic table. A preliminary overview is provided on the reactivity of carbon dioxide with amines, and emphasis is given to recent findings concerning applications in various fields. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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23 pages, 6905 KiB  
Review
The Coordination Chemistry of Bio-Relevant Ligands and Their Magnesium Complexes
by Derek R. Case, Jon Zubieta and Robert P. Doyle
Molecules 2020, 25(14), 3172; https://doi.org/10.3390/molecules25143172 - 11 Jul 2020
Cited by 19 | Viewed by 6918
Abstract
The coordination chemistry of magnesium (Mg2+) was extensively explored. More recently; magnesium; which plays a role in over 80% of metabolic functions and governs over 350 enzymatic processes; is becoming increasingly linked to chronic disease—predominantly due to magnesium deficiency (hypomagnesemia). Supplemental [...] Read more.
The coordination chemistry of magnesium (Mg2+) was extensively explored. More recently; magnesium; which plays a role in over 80% of metabolic functions and governs over 350 enzymatic processes; is becoming increasingly linked to chronic disease—predominantly due to magnesium deficiency (hypomagnesemia). Supplemental dietary magnesium utilizing biorelevant chelate ligands is a proven method for counteracting hypomagnesemia. However, the coordination chemistry of such bio-relevant magnesium complexes is yet to be extensively explored or elucidated. It is the aim of this review to comprehensively describe what is currently known about common bio-relevant magnesium complexes from the perspective of coordination chemistry. Full article
(This article belongs to the Special Issue Advances in Coordination Chemistry)
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