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1

Lamberts, Kevin, Andreas Möller et Ulli Englert. « Enantiopure and racemic alanine as bridging ligands in Ca and Mn chain polymers ». Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials 70, no 6 (1 décembre 2014) : 989–98. http://dx.doi.org/10.1107/s2052520614021398.

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Under accelerated and controlled evaporation, chain polymers crystallize from aqueous solutions of CaIIand MnIIhalides with enantiopure L-alanine or racemic DL-alanine. In all ten solids thus obtained zwitterionic amino acid ligands bridge neighbouring cations. The exclusively O-donor-based coordination sphere around the metal cations is completed by aqua ligands; the halides remain uncoordinated and act as counter-anions for the cationic strands. Despite the differences in ionic radii and electronic structure between the main group and the transition metal cation, their derivatives with L-alanine share a common structure type. In contrast, the solids derived from DL-alanine differ and adopt structures depending on the metal cation and the halide. Homochiral chains of either chirality or heterochiral chains with different arrangements of crystallographic inversion centres along the polymer strands are encountered. On average, the six-coordinated CaIIcations, devoid of any ligand field effect, show more pronounced deviation from idealized octahedral geometry than thed-block cation MnII.
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2

Ogura, Yusaku, Masahiro Nakano, Hajime Maeda, Masahito Segi et Taniyuki Furuyama. « Cationic Axial Ligand Effects on Sulfur-Substituted Subphthalocyanines ». Molecules 27, no 9 (26 avril 2022) : 2766. http://dx.doi.org/10.3390/molecules27092766.

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Herein, we report the synthesis of sulfur-substituted boron(III) subphthalocyanines (SubPcs) with cationic axial ligands. Subphthalocyanines were synthesized by a condensation reaction using the corresponding phthalonitriles and boron trichloride as a template. An aminoalkyl group was introduced on the central boron atom; this process was followed by N-methylation to introduce a cationic axial ligand. The peripheral sulfur groups shifted the Q band of SubPcs to a longer wavelength. The cationic axial ligands increased the polarity and enhanced the hydrophilicity of SubPcs. The effect of axial ligands on absorption and fluorescence properties is generally small. However, a further red shift was observed by introducing cationic axial ligands into the sulfur-substituted SubPcs. This change is similar to that in sulfur-substituted silicon(IV) phthalocyanines. The unique effect of the cationic axial ligand was extensively investigated by theoretical calculations and electrochemistry. In particular, the precise oxidation potential was determined using ionization potential measurements. Thus, the results of the present study provide a novel strategy for developing functional dyes and pigments based on SubPcs.
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3

Wright, Stephen H. « Molecular and cellular physiology of organic cation transporter 2 ». American Journal of Physiology-Renal Physiology 317, no 6 (1 décembre 2019) : F1669—F1679. http://dx.doi.org/10.1152/ajprenal.00422.2019.

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Organic cation transporters play a critical role in mediating the distribution of cationic pharmaceuticals. Indeed, organic cation transporter (OCT)2 is the initial step in the renal secretion of organic cations and consequently plays a defining role in establishing the pharmacokinetics of many cationic drugs. Although a hallmark of OCTs is their broad selectivity, this characteristic also makes them targets for unwanted, adverse drug-drug interactions (DDIs), making them a focus for efforts to develop models of ligand interaction that could predict and preempt these adverse interactions. This review discusses the molecular characteristics of these transporters as well as the evidence that established the OCTs as key players in the distribution of organic cations. However, the primary focus is the present understanding of the complexity of ligand interaction with OCTs, particularly OCT2, including evidence for the presence of multiple ligand-binding sites and the influence of substrate structure on the affinity of the transporter for inhibitory ligands. This leads to a discussion of the complexities associated with the development of protocols for assessing the inhibitory potential of new molecular entities to perpetrate unwanted DDIs, the criteria that should be considered in the interpretation of the results of such protocols, and the challenges associated with development of models capable of predicting unwanted DDIs.
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Babukutty, Leslie, Ethan Moskovic, Davina Wadler, Thomas Strekas et Robert Engel. « Polycations XX : New Monodentate Cationic Ligands and Their Coordination with Ruthenium for the Construction of Complexes Expressing Enhanced Interaction with DNA ». Organic Chemistry International 2012 (15 octobre 2012) : 1–7. http://dx.doi.org/10.1155/2012/282137.

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Prior investigations from this laboratory concerned with the preparation of new types of organic cations for a variety of biological and nonbiological applications have been extended to the preparation of cation-bearing ligands with nitrogen coordinating sites for use in complexation reactions with ruthenium cores. The syntheses of new cationic ligands as well as ruthenium complexes bearing them are reported here. The introduction of these new types of ligands is intended to provide to the complexes an enhanced ability to interact with DNA, and thereby to have the potential to be enhanced antitumor agents. Preliminary observations of their interactions with DNA are presented.
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Zeng, Juxiang, Guodong Tang et Jun Qian. « Synthesis and crystal structure of (1,10-phenanthroline-κ2 N,N′)[2-(1H-pyrazol-1-yl)phenyl-κ2 N 2,C 1]iridium(III) hexafluoridophosphate with an unknown number of solvent molecules ». Acta Crystallographica Section E Crystallographic Communications 76, no 6 (5 mai 2020) : 803–6. http://dx.doi.org/10.1107/s2056989020005861.

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The cationic complex in the title compound, [Ir(C9H7N2)2(C12H8N2)]PF6, comprises two phenylpyrazole (ppz) cyclometallating ligands and one 1,10-phenanthroline (phen) ancillary ligand. The asymmetric unit consists of one [Ir(ppz)2(phen)]+ cation and one [PF6]− counter-ion. The central IrIII ion is six-coordinated by two N atoms and two C atoms from the two ppz ligands as well as by two N atoms from the phen ligand within a distorted octahedral C2N4 coordination set. In the crystal structure, the [Ir(ppz)2(phen)]+ cations and PF6 − counter-ions are connected with each other through weak intermolecular C—H...F hydrogen bonds. Additional C—H...π interactions between the rings of neighbouring cations consolidate the three-dimensional network. Electron density associated with additional disordered solvent molecules inside cavities of the structure was removed with the SQUEEZE procedure in PLATON [Spek (2015). Acta Cryst. C71, 9–18]. The given chemical formula and other crystal data do not take into account the unknown solvent molecule(s). The title compound has a different space-group symmetry (C2/c) from its solvatomorph (P21/c) comprising 1.5CH2Cl2 solvent molecules per ion pair.
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Mbiangué, Yves Alain, Alfred Bijvédé, Patrice Kenfack Tsobnang, Emmanuel Wenger et Claude Lecomte. « Crystal structure of diammonium bis[tris(oxamide dioxime-κ2 N,N′)nickel(II)] bis[tris(oxalato-κ2 O,O′)chromate(III)] 6.76-hydrate ». Acta Crystallographica Section E Crystallographic Communications 76, no 11 (9 octobre 2020) : 1732–36. http://dx.doi.org/10.1107/s2056989020013390.

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The asymmetric unit of the title compound, (NH4)2[Ni(C2H6N4O2)3]2[Cr(C2O4)3]2·6.76H2O, comprises two NH4 + cations, two [Ni(C2H6N4O2)3]2+ cations and two [Cr(C2O4)3]3– anions, as well as eight water molecules of crystallization of which only one is fully occupied. In the cationic and anionic complexes, the central atoms (NiII and CrIII) are each surrounded by three bidentate ligands (N-chelating oxamide dioxime and O-chelating oxalate, respectively), resulting in distorted octahedral coordination spheres. In the crystal, O—H...O hydrogen bonds between the oxamide dioxime ligands as donor groups and the oxalate ligands as acceptor groups alternately connect the cationic and anionic complexes into infinite pillars extending parallel to [100]. Moreover, N—H...O hydrogen bonds between the same ligands connect neighboring pillars, thus delineating channels that accommodate the charge-balancing NH4 + cations as well as the water molecules of crystallization. Although the H atoms could not be localized for these two species, the corresponding N...O and O...O distances indicate hydrogen bonds of medium strength.
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7

Santiago, Tomás G., Carmen Urbaneja, Eleuterio Álvarez, Elena Ávila, Pilar Palma et Juan Cámpora. « Neutral, cationic and anionic organonickel and -palladium complexes supported by iminophosphine/phosphinoenaminato ligands ». Dalton Transactions 49, no 2 (2020) : 322–35. http://dx.doi.org/10.1039/c9dt04062e.

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Ligand exchange and oxidative addition reactions allow the synthesis of Ni(ii) and Pd(ii) complexes with deprotonable iminophosphine ligands. The acid–base behavior of iminophosphine ligands coordinated to organometallic Ni(ii) fragments is analyzed.
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8

Rahimi, Naser, et Davit Zargarian. « Cationic tetra- and pentacoordinate complexes of nickel based on POCN- and POCOP-type pincer ligands : synthesis, characterization, and ligand exchange studies ». New Journal of Chemistry 45, no 33 (2021) : 15063–73. http://dx.doi.org/10.1039/d1nj01355f.

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The closely related pincer ligands POCN and POCOP display different electron donating properties and different degrees of resistance to ligand exchange reactions proceeding via cationic reaction intermediates.
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9

Wagler, Jörg, Uwe Böhme, Erica Brendler et Gerhard Roewer. « First X-Ray Structure of a Cationic Silicon Complex with Salen-Type Ligand : An Unusual Compound with Two Different Si-N Dative Bonds ». Zeitschrift für Naturforschung B 59, no 11-12 (1 décembre 2004) : 1348–52. http://dx.doi.org/10.1515/znb-2004-11-1255.

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Abstract Two novel compounds containing pentacoordinate alkylsiliconium-cations with an 〈O, N, O 〉- chelating ligand of salen-type were prepared by reacting the trimethylsilyl derivatives of the ligand with alkyltrichlorosilanes. Pentacoordination of the silicon atom is found in solid state as well as in solution. Crystals of compound 2a, ethylene-N, N’ -bis(2-oxy-4-methoxybenzophenoneiminato) methylsiliconium chloride, were obtained from chloroform solution. This complex crystallizes in monoclinic space group P21/n. The chloride ion is surrounded by three chloroform molecules in the solid state. The siliconium cation has trigonal bipyramidal geometry in the solid state, although the signals of two chemically equal half-sides of the salen-type ligand were revealed in 1H and 13C NMR spectra of its chloroform solution. Therefrom two different Si-N dative bonds within the same molecule arise. The reaction of methyltrichlorosilane with two non-linked “half-ligands” of the salen-type leads also to a siliconium complex with similar cationic coordination sphere motif.
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10

Schenk, Wolfdieter A., Ute Karl et Michael R. Horn. « Kationische Schwefeldioxid-Komplexe des Eisens und Rutheniums vom Halbsandwich-Typ [1] / Cationic Halfsandwich-Type Sulfur Dioxide Complexes of Iron and Ruthenium [1] ». Zeitschrift für Naturforschung B 44, no 12 (1 décembre 1989) : 1513–18. http://dx.doi.org/10.1515/znb-1989-1208.

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Cationic halfsandwich-type complexes of sulfur dioxide, [C5R5M(PR3)2(SO2)]+ (R = H, Me, M = Fe, Ru, (PR3)2 = mono- or bidentate phosphorus ligands) and [C5Me5Fe(CO)(PR3)(SO2)]+, are obtained by ligand exchange from labile cationic (M = Fe) or neutral (M = Ru) precursors. The new compounds are characterized by IR, 1H131H, 13C and 31P NMR spectroscopy. Their stability increases with increasing electron density at the metal.
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11

Zhou, Qin-Qin, Lei Jin, Wei-Qiang Liao et Yi Zhang. « A potential molecular ferroelectric material : poly[[bis(1-aza-4-azoniabicyclo[2.2.2]octane)di-μ3-chlorido-tetra-μ2-chlorido-dichloridotricadmium(II)] dihydrate] ». Acta Crystallographica Section C Crystal Structure Communications 69, no 3 (16 février 2013) : 237–40. http://dx.doi.org/10.1107/s0108270113003892.

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The title compound, {[Cd3(C6H13N2)2Cl8]·2H2O}n, consists of pendant protonated cationic diamine ligands bonded to an anionic one-dimensional coordination polymer chloridocadmate scaffold. Each coordination chain features two kinds of CdIIcentre, each with distorted octahedral coordination geometry. One CdIIcation lies on a centre of inversion and is coordinated by six bridging chloride ligands, while the other is coordinated by four bridging chloride ligands, one terminal chloride ligand and a 1-aza-4-azoniabicyclo[2.2.2]octane aza N atom. This gives a reversible corner-sharing half-cubic linear polymer that lies along the crystallographicadirection. The chains interact through hydrogen bonding with solvent water, with each water molecule accepting one N—H...O interaction from a cation and donating to two O—H...Cl interactions with anionic chains, thus linking three separate chains and completing the packing structure.
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12

Cuza, Emmelyne, Samia Benmansour, Nathalie Cosquer, Françoise Conan, Sébastien Pillet, Carlos J. Gómez-García et Smail Triki. « Spin Cross-Over (SCO) Anionic Fe(II) Complexes Based on the Tripodal Ligand Tris(2-pyridyl)ethoxymethane ». Magnetochemistry 6, no 2 (7 juin 2020) : 26. http://dx.doi.org/10.3390/magnetochemistry6020026.

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Reactions of Fe(II) with the tripodal chelating ligand 1,1,1-tris(2-pyridyl)ethoxymethane (py3C-OEt) and (NCE)− co-ligands (E = S, Se, BH3) give a series of mononuclear complexes formulated as [Fe(py3C-OEt)2][Fe(py3C-OEt)(NCE)3]2·2CH3CN, with E = S (1) and BH3 (2). These compounds are the first Fe(II) spin cross-over (SCO) complexes based on the tripodal ligand tris(2-pyridyl)ethoxymethane and on the versatile co-ligands (NCS)− and (NCBH3)−. The crystal structure reveals discrete monomeric isomorph structures formed by a cationic [Fe(py3C-OEt)2]2+ complex and by two equivalent anionic [Fe(py3C-OEt)(NCE)3]− complexes. In the cations the Fe(II) is facially coordinated by two py3C-OEt tripodal ligands whereas in the anion the three nitrogen atoms of the tripodal ligand are facially coordinated and the N-donor atoms of the three (NCE)− co-ligands occupy the remaining three positions to complete the distorted octahedral environment of the Fe(II) centre. The magnetic studies show the presence of gradual SCO for both complexes: A one-step transition around 205 K for 1 and a two-step transition for compound 2, centered around 245 K and 380 K.
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13

Bröring, Martin, Carsten D. Brandt, Silke Köhler et Maximilian Sieber. « Crystallographic evidence for structural diversity in cationic (tripyrrinato)cobalt(II) complexes ». Journal of Porphyrins and Phthalocyanines 09, no 10 (octobre 2005) : 683–90. http://dx.doi.org/10.1142/s1088424605000794.

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Cobalt(II) complexes of tripyrrin ligands can be transformed into cations by anion exchange using NaBAr F , a salt of a weakly coordinating anion. The complete characterization of these highly sensitive cations (probably solvate complexes) could not be achieved, but the coordination to donor ligands like nitriles or trialkylphosphanes stabilizes the cations sufficiently for the isolation of some single crystals. As the structural analyses of these donor-stabilized cobalt(II) tripyrrins reveal, either four- or five coordinate structures are formed depending on the type and size of ligand used.
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14

Kilic, Ahmet, Eyyup Yasar et Emine Aytar. « Neutral boron [(L1-3)BPh2] and cationic charged boron [(L1a-3a)BPh2] complexes for chemical CO2 conversion to obtain cyclic carbonates under ambient conditions ». Sustainable Energy & ; Fuels 3, no 4 (2019) : 1066–77. http://dx.doi.org/10.1039/c8se00633d.

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Three neutral salen ligands (L1-3) with three cationic charged salen ligands (L1a-3a) and the corresponding neutral boron [(L1-3)BPh2] and cationic charged boron [(L1a-3a)BPh2] compounds have been successfully synthesized and characterized under ambient conditions.
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15

Son, Jung-Su, Sung-Chul Lim, Hochun Lee et Seung-Tae Hong. « Crystal structure ofcatena-poly[[[diaquacobalt(II)]-bis(μ-hex-3-enedinitrile-κ2N:N′)] bis(tetrafluoridoborate)] ». Acta Crystallographica Section E Crystallographic Communications 71, no 6 (23 mai 2015) : m135—m136. http://dx.doi.org/10.1107/s2056989015009548.

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In the structure of the title salt, [Co(C6H6N2)2(H2O)2](BF4)2, the CoIIatom is located on an inversion centre. The transition metal is in a slightly distorted octahedral coordination environment, defined by the cyano N atoms of four hex-3-enedinitrile ligands in equatorial positions and the O atoms of two water molecules in axial positions. The bridging mode of the hex-3-enedinitrile ligands leads to the formation of cationic chains extending parallel to [1-10]. The BF4−counter-anion is disordered over two sets of sites [occupancy ratio = 0.512 (19):0.489 (19)]. It is located in the voids between the cationic chains and is connected to the aqua ligands of the latter through O—H...F hydrogen bonds. One methylene H atom of the hex-3-enedinitrile ligand forms another and weak C—H...O hydrogen bond with a water O atom of a neighbouring chain, thus consolidating the three-dimensional network structure.
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Wang, Yanlan, Anna Monfredini, Pierre-Alexandre Deyris, Florent Blanchard, Etienne Derat, Giovanni Maestri et Max Malacria. « All-metal aromatic cationic palladium triangles can mimic aromatic donor ligands with Lewis acidic cations ». Chem. Sci. 8, no 11 (2017) : 7394–402. http://dx.doi.org/10.1039/c7sc03475j.

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Terwingen, Steven van, et Ulli Englert. « Argentophilic Interactions in Two AgI Complexes of 3-(2-(Pyridin-4-yl)ethyl)pentane-2,4-dione, a Promising Ditopic Ligand ». Crystals 9, no 8 (9 août 2019) : 414. http://dx.doi.org/10.3390/cryst9080414.

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Reactions of 3-(2-(pyridin-4-yl)ethyl)pentane-2,4-dione (HacacPyen) with AgPF6 and AgBF4 afforded cationic silver complexes [Ag(HacacPyen)2]+ with essentially linear coordination of the Ag I cation by two pyridine N atoms. Rather unexpectedly, the HacacPyen ligands in the PF6- salt 1 adopt the diketo form, in contrast to the uncoordinated HacacPyen molecule, whereas the corresponding BF4- salt 2 and the majority of 3-substituted acetylacetones crystallizes as the enol tautomer. In both compounds 1 and 2, complex cations aggregate via short Ag...Ag interactions to pairs. These contacts amount to 3 . 21 Å in 1 and 3 . 26 Å or 3 . 31 Å in 2. As they are unsupported by any additional bridging ligands and correspond to the closest interionic interactions between neighbouring complex cations, they may be addressed as argentophilic interactions. The PF6- anions in 1 and the BF4- counter ions in 2 are involved in long and presumably electrostatic Ag...F contacts of ca. 2 . 9 Å. Additional coordination between Ag I and keto O atoms of symmetry-equivalent ligands occurs in 1 and leads to an extended two-periodic supramolecular structure.
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Ju-Nam, Yon, Wanisa Abdussalam-Mohammed et Jesus J. Ojeda. « Highly stable noble metal nanoparticles dispersible in biocompatible solvents : synthesis of cationic phosphonium gold nanoparticles in water and DMSO ». Faraday Discussions 186 (2016) : 77–93. http://dx.doi.org/10.1039/c5fd00131e.

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In this work, we report the synthesis of novel cationic phosphonium gold nanoparticles dispersible in water and dimethyl sulfoxide (DMSO) for their potential use in biomedical applications. All the cationic-functionalising ligands currently reported in the literature are ammonium-based species. Here, the synthesis and characterisation of an alternative system, based on phosphonioalkylthiosulfate zwitterions and phosphonioalkylthioacetate were carried out. We have also demonstrated that our phosphonioalkylthiosulfate zwitterions readily disproportionate into phosphonioalkylthiolates in situ during the synthesis of gold nanoparticles produced by the borohydride reduction of gold(iii) salts. The synthesis of the cationic gold nanoparticles using these phosphonium ligands was carried out in water and DMSO. UV-visible spectroscopic and TEM studies have shown that the phosphonioalkylthiolates bind to the surface of gold nanoparticles which are typically around 10 nm in diameter. The resulting cationic-functionalised gold nanoparticles are dispersible in aqueous media and in DMSO, which is the only organic solvent approved by the U.S. Food and Drug Administration (FDA) for drug carrier tests. This indicates their potential future use in biological applications. This work shows the synthesis of a new family of phosphonium-based ligands, which behave as cationic masked thiolate ligands in the functionalisation of gold nanoparticles. These highly stable colloidal cationic phosphonium gold nanoparticles dispersed in water and DMSO can offer a great opportunity for the design of novel biorecognition and drug delivery systems.
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McKinty, Adam M., et Douglas W. Stephan. « Ru alkylidene compounds bearing tridentate, dianionic ligands : Lewis acid activation and olefin metathesis ». Dalton Transactions 45, no 9 (2016) : 3844–52. http://dx.doi.org/10.1039/c5dt04481b.

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The series of tridentate complexes were prepared and shown to react with BCl3 to give the complexes affording neutral and cationic complexes sequentially. The generated five coordinate cations were evaluated in standard preliminary tests for olefin metathesis catalysis.
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Xanthopoulos, Konstantinos, Zafeiria Anagnostou, Sophocles Chalkiadakis, Duane Choquesillo-Lazarte, Gellert Mezei, Jan K. Zaręba, Jerzy Zoń et Konstantinos D. Demadis. « Platonic Relationships in Metal Phosphonate Chemistry : Ionic Metal Phosphonates ». Crystals 9, no 6 (11 juin 2019) : 301. http://dx.doi.org/10.3390/cryst9060301.

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Phosphonate ligands demonstrate strong affinity for metal ions. However, there are several cases where the phosphonate is found non-coordinated to the metal ion. Such compounds could be characterized as salts, since the interactions involved are ionic and hydrogen bonding. In this paper we explore a number of such examples, using divalent metal ions (Mg2+, Ca2+, Sr2+ and Ni2+) and the phosphonic acids: p-aminobenzylphosphonic acid (H2PABPA), tetramethylenediamine-tetrakis(methylenephosphonic acid) (H8TDTMP), and 1,2-ethylenediphosphonic acid (H4EDPA). The compounds isolated and structurally characterized are [Mg(H2O)6]·[HPABPA]2·6H2O, [Ca(H2O)8]·[HPABPA]2, [Sr(H2O)8]·[HPABPA]2, [Mg(H2O)6]·[H6TDTMP], and [Ni(H2O)6]·[H2EDPA]·H2O. Also, the coordination polymer {[Ni(4,4’-bpy)(H2O)4]·[H2EDPA]·H2O}n was synthesized and characterized, which contains a bridging 4,4’-bipyridine (4,4’-bpy) ligand forming an infinite chain with the Ni2+ cations. All these compounds contain the phosphonate anion as the counterion to charge balance the cationic charge originating from the metal cation.
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Henwood, Adam F., Ashu K. Bansal, David B. Cordes, Alexandra M. Z. Slawin, Ifor D. W. Samuel et Eli Zysman-Colman. « Solubilised bright blue-emitting iridium complexes for solution processed OLEDs ». Journal of Materials Chemistry C 4, no 17 (2016) : 3726–37. http://dx.doi.org/10.1039/c6tc00151c.

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Combining a sterically bulky, electron-deficient cyclometalating CN ligands with an electron rich, highly rigidified NN ligand gives an iridium complex, that achieves extraordinarily bright blue emission (ΦPL = 90%; λmax = 459 nm in MeCN) for a cationic iridium complex.
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Delpech, Fabien, Ilia A. Guzei et Richard F. Jordan. « Cationic Indium Alkyl Complexes Incorporating Aminotroponiminate Ligands ». Organometallics 21, no 6 (mars 2002) : 1167–76. http://dx.doi.org/10.1021/om010578x.

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Endo, Koji, et Robert H. Grubbs. « Cationic ruthenium alkylidene catalysts bearing phosphine ligands ». Dalton Transactions 45, no 8 (2016) : 3627–34. http://dx.doi.org/10.1039/c5dt04506a.

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Tanaka, Kimiya, Makoto Tanabe, Tomohito Ide et Kohtaro Osakada. « Cationic Hydridotriplatinum Complex with Bridging Germylene Ligands ». Organometallics 33, no 10 (7 mai 2014) : 2608–12. http://dx.doi.org/10.1021/om500309k.

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Korolev, Andrey V., Eiji Ihara, Ilia A. Guzei, Victor G. Young, et Richard F. Jordan. « Cationic Aluminum Alkyl Complexes Incorporating Aminotroponiminate Ligands ». Journal of the American Chemical Society 123, no 34 (août 2001) : 8291–309. http://dx.doi.org/10.1021/ja010242e.

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Ihara, Eiji, Victor G. Young, et Richard F. Jordan. « Cationic Aluminum Alkyl Complexes Incorporating Aminotroponiminate Ligands ». Journal of the American Chemical Society 120, no 32 (août 1998) : 8277–78. http://dx.doi.org/10.1021/ja9817444.

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Louie, Brenda M., Steven J. Rettig, Alan Storr et James Trotter. « Rhenium and manganese carbonyl compounds incorporating tridentate chelating pyrazolyl gallate ligands ». Canadian Journal of Chemistry 63, no 8 (1 août 1985) : 2261–72. http://dx.doi.org/10.1139/v85-373.

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The coordinating properties of a variety of unsymmetrical uninegative tridentate chelating "pyrazolylgallate" ligands have been studied using the tricarbonyl moieties "M(CO)3", where M = Mn or Re, as acceptor species. A series of monomeric, pseudo octahedral complexes has been characterized and a fac mode of coordination established for the tridentate gallate ligands from 1H nmr, ir measurements, and X-ray structure determinations. Nitrosylation of a selection of the rhenium tricarbonyl compounds has yielded a number of cationic rhenium mononitrosyl dicarbonyl species. The reactivity of these cations towards reducing agents has been investigated.
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Parshina, Yu P., T. A. Kovylina, A. N. Konev, A. A. Belikov, P. O. Baber, A. D. Komarova, E. A. Romaeva et L. N. Bochkarev. « Norbornene-Substituted Cationic Iridium(III) Complex and Water-Soluble Luminescent Polymers Based on It : Synthesis, Photophysical and Cytotoxic Properties ». Russian Journal of General Chemistry 92, no 12 (décembre 2022) : 2666–75. http://dx.doi.org/10.1134/s1070363222120167.

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Abstract A norbornene-substituted cationic iridium(III) complex containing 1-phenylisoquinoline cyclometalating ligands and an additional phenylimidazophenanthroline ligand was synthesized. On the base of this complex, water-soluble polymers were obtained by ring-opening metathesis polymerization (ROMP). The resulting polymers showed oxygen-dependent phosphorescence in the orange spectral region and high cytotoxicity against HCT116 cancer cells.
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29

Shutkov, Ilya A., Yulia N. Okulova, Dmitrii M. Mazur, Nikolai A. Melnichuk, Denis A. Babkov, Elena V. Sokolova, Alexander A. Spasov, Elena R. Milaeva et Alexey A. Nazarov. « New Organometallic Ru(II) Compounds with Lonidamine Motif as Antitumor Agents ». Pharmaceutics 15, no 5 (29 avril 2023) : 1366. http://dx.doi.org/10.3390/pharmaceutics15051366.

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The combination of one molecule of organic and metal-based fragments that exhibit antitumor activity is a modern approach in the search for new promising drugs. In this work, biologically active ligands based on lonidamine (a selective inhibitor of aerobic glycolysis used in clinical practice) were introduced into the structure of an antitumor organometallic ruthenium scaffold. Resistant to ligand exchange reactions, compounds were prepared by replacing labile ligands with stable ones. Moreover, cationic complexes containing two lonidamine-based ligands were obtained. Antiproliferative activity was studied in vitro by MTT assays. It was shown that the increase in the stability in ligand exchange reactions does not influence cytotoxicity. At the same time, the introduction of the second lonidamine fragment approximately doubles the cytotoxicity of studied complexes. The ability to induce apoptosis and caspase activation in tumour cell MCF7 was studied by employing flow cytometry.
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30

Chen, Xun, Steven Stout, Uwe Mueller, George Boykow, Richard Visconti, Phieng Siliphaivanh, Kerrie Spencer et al. « Label-Free, LC-MS-Based Assays to Quantitate Small-Molecule Antagonist Binding to the Mammalian BLT1 Receptor ». SLAS DISCOVERY : Advancing the Science of Drug Discovery 22, no 9 (1 août 2017) : 1131–41. http://dx.doi.org/10.1177/2472555217719748.

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We have developed and validated label-free, liquid chromatography–mass spectrometry (LC-MS)-based equilibrium direct and competition binding assays to quantitate small-molecule antagonist binding to recombinant human and mouse BLT1 receptors expressed in HEK 293 cell membranes. Procedurally, these binding assays involve (1) equilibration of the BLT1 receptor and probe ligand, with or without a competitor; (2) vacuum filtration through cationic glass fiber filters to separate receptor-bound from free probe ligand; and (3) LC-MS analysis in selected reaction monitoring mode for bound probe ligand quantitation. Two novel, optimized probe ligands, compounds 1 and 2, were identified by screening 20 unlabeled BLT1 antagonists for direct binding. Saturation direct binding studies confirmed the high affinity, and dissociation studies established the rapid binding kinetics of probe ligands 1 and 2. Competition binding assays were established using both probe ligands, and the affinities of structurally diverse BLT1 antagonists were measured. Both binding assay formats can be executed with high specificity and sensitivity and moderate throughput (96-well plate format) using these approaches. This highly versatile, label-free method for studying ligand binding to membrane-associated receptors should find broad application as an alternative to traditional methods using labeled ligands.
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31

Edwards, Gavin L., David St C. Black, Glen B. Deacon et Laurence PG Wakelin. « Effect of charge and surface area on the cytotoxicity of cationic metallointercalation reagents ». Canadian Journal of Chemistry 83, no 6-7 (1 juin 2005) : 969–79. http://dx.doi.org/10.1139/v05-110.

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Reaction of a series of nitrogen donor ligands (1-phenylpyrazoles, 2-phenylpyridine, benzo[h]quinoline, 1-(2′-pyridyl)indole, 1-phenylindazole, and 2-phenylindazole) with palladium(II) and platinum(II) salts gave complexes where ortho-metallation had occurred resulting in bidentate binding to the metal centres through N and C atoms. These cyclometallated products were isolated as µ-chloro dimers. Subsequent treatment of these µ-chloro dimers with chelating diamines such as 1,2-ethanediamine converted them into 14 cationic (1+) complexes. Analogous coordination mixed ligand complexes (charge 2+) were prepared by reaction of dichloro(1,2-ethanediamine-N,N′)palladium(II) with aromatic diamines such as 2-(1′-pyrazolyl)pyridine, 2,2′-bipyridine, and 1,10-phenanthroline. The complexes exhibited growth inhibitory activity against L1210 mouse leukæmia cells in vitro over a wide concentration range; in general, the cyclometallated complexes were more active than the mixed ligand complexes, although one cyclometallated organoplatinum complex was less active than the mixed ligand analogue. Substitution around the periphery of the aromatic ligands also resulted in increased activity. One complex, derived from 1-(2'-pyridyl)indole, was tested in vivo and showed no significant antitumour inhibition against P388 leukæmia at doses below toxic levels. Key words: anticancer, metallointercalator, cyclometallation, palladium, platinum, cytotoxicity.
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32

Friese, Seth J., Samantha A. Labb, Conner J. Masteran, Savannah G. Albright, Bakr Ali, Hayley A. Chapman, Yijie Cheng et al. « Synthesis of a Water-Soluble, Soft N-Donor BTzBP Ligand Containing Only CHON ». Synlett 31, no 14 (24 juin 2020) : 1384–88. http://dx.doi.org/10.1055/s-0040-1707163.

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A hydrophilic ligand that contains only C, H, O, and N substituents and uses a 6,6′-bis(1H-1,2,3-triazol-4-yl)-2,2′-bipyridine (BTzBP) structural core has been synthesized. The effect of adding water-soluble groups onto extractant ligands has been extensively studied to facilitate the efficient partitioning of 4f and transuranic 5f elements for the treatment of spent nuclear fuel. Soft, N-donor ligands exhibit greater binding affinities for the trivalent actinides over the trivalent lanthanides, making BTzBP ligands an ideal candidate in the search for extractants to be used on an industrial scale. To date, hydrophobic BTzBPs have been shown to exhibit physical and chemical properties that might be conducive to nuclear waste processing conditions. However, hydrophilic BTzBPs have yet to be reported. Herein, we show the synthesis of a hydrophilic BTzBP ligand featuring cationic water solubilizing groups attached to the bipyridal rings.
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33

Tikhonov, D. B., L. G. Magazanik et E. I. Nagaeva. « Ligands of Acid-Sensing Ion Channel 1a : Mechanisms of Action and Binding Sites ». Acta Naturae 11, no 1 (15 mars 2019) : 4–13. http://dx.doi.org/10.32607/20758251-2019-11-1-4-13.

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The proton-gated cationic channels belonging to the ASIC family are widely distributed in the central nervous system of vertebrates and play an important role in several physiological and pathological processes. ASIC1a are most sensitive to acidification of the external medium, which is the reason for the current interest in their function and pharmacology. Recently, the list of ASIC1a ligands has been rapidly expanding. It includes inorganic cations, a large number of synthetic and endogenous small molecules, and peptide toxins. The information on the mechanisms of action and the binding sites of the ligands comes from electrophysiological, mutational and structural studies. In the present review, we attempt to present a systematic view of the complex pattern of interactions between ligands and ASIC1a.
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34

Xu, Li-Qing, Li-Ping Lu et Miao-Li Zhu. « Analogy to a Chinese knot in an ion-pair copper(II)–neodymium(III) complex based on a hexadentate Schiff base condensation product of 5-bromosalicylaldehyde and glycylglycine ». Acta Crystallographica Section C Crystal Structure Communications 69, no 4 (14 mars 2013) : 376–79. http://dx.doi.org/10.1107/s0108270113006367.

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Self-assembly of CuCl2, NdCl3, 5-bromosalicylaldehyde and glycylglycine yields the ion-pair copper(II)–neodymium(III) complex, poly[[decaaquabis[μ3-2-({2-[(5-bromo-2-oxidobenzylidene)amino]acetyl}azanidyl)acetato]bis[μ2-2-({2-[(5-bromo-2-oxidobenzylidene)amino]acetyl}azanidyl)acetato]tetracopper(II)dineodymium(III)] bis{[2-({2-[(5-bromo-2-oxidobenzylidene)amino]acetyl}azanidyl)acetato]cuprate(II)} tetradecahydrate], {[Cu4Nd2(C11H8BrN2O4)4(H2O)10][Cu(C11H8BrN2O4)]2·14H2O}n. The anion is planar and mononuclear, showing an approximately square-planar coordination of the metal atom, while the cation is a hexanuclear centrosymmetric transition metal–lanthanide (Cu–Nd) heterometallic complex, with the independent copper cations in square-planar and square-pyramidal coordinations. The asymmetric unit comprises one half of this cation, one anion and seven solvent water molecules. The positions of the six metal centres in the cation reproduce a Chinese knot arrangement. The dipeptidic Schiff base releases three H atoms and can act as a tetradentate, a pentadentate or a hexadentate ligand. Longer interactions between the pentadentate ligands and the Jahn–Teller CuIIcation link the hexanuclear aggregates into cationic chains in the [010] direction in which 14- and 22-membered subloops occur. Extensive hydrogen bonding in three dimensions involves both the coordinated and the solvent water molecules.
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35

Egorova, B. V., O. A. Fedorova et S. N. Kalmykov. « Cationic radionuclides and ligands for targeted therapeutic radiopharmaceuticals ». Russian Chemical Reviews 88, no 9 (3 septembre 2019) : 901–24. http://dx.doi.org/10.1070/rcr4890.

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36

Liu, Shengming, Miguel-Angel Munoz-Hernandez et David A. Atwood. « Bimetallic and cationic aluminum with N3O2 chelate ligands ». Journal of Organometallic Chemistry 596, no 1-2 (février 2000) : 109–14. http://dx.doi.org/10.1016/s0022-328x(99)00575-6.

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37

Gopinathan, Sarada, S. S. Deshpande et C. Gopinathan. « Cationic Ruthenium(II) Carbonyl Complexes with Nitrile Ligands ». Zeitschrift f�r anorganische und allgemeine Chemie 527, no 8 (août 1985) : 203–7. http://dx.doi.org/10.1002/zaac.19855270823.

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38

Zhang, Chenghui, Libo Sun, Chuanqi Zhang, Song Wan, Zhiqiang Liang et Jiyang Li. « Novel photo- and/or thermochromic MOFs derived from bipyridinium carboxylate ligands ». Inorganic Chemistry Frontiers 3, no 6 (2016) : 814–20. http://dx.doi.org/10.1039/c6qi00013d.

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Two new Zn-MOFs based on 1-(3,5-dicarboxyphenyl)-4,4′-bipyridinium bromide have been synthesized. Compound 1 has a 3D interpenetrated cationic framework with photo- and thermochromism, while compound 2 possesses a 2D layered cationic network with only photochromism.
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39

Laurie, J. C. V., L. Duncan, R. C. Haltiwanger, R. T. Weberg et Mary Rakowski DuBois. « Activation of hydrogen by cationic cyclopentadienylmolybdenum dimers with sulfido ligands. 1. Cationic complexes derived from protonation of 1,2-alkenedithiolate ligands ». Journal of the American Chemical Society 108, no 20 (octobre 1986) : 6234–41. http://dx.doi.org/10.1021/ja00280a021.

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40

Knauer, Lena, Michael Knorr, Lydie Viau et Carsten Strohmann. « Crystal structure of the coordination polymer catena-poly[[[(acetonitrile-κN)copper(I)]-μ3-1,3-dithiolane-κ3 S:S:S′] hexafluoridophosphate] ». Acta Crystallographica Section E Crystallographic Communications 76, no 1 (1 janvier 2020) : 38–41. http://dx.doi.org/10.1107/s205698901901627x.

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The polymeric title compound, [Cu2(C2H3N)2(C3H6S2)2](PF6)2, represents an example of a one-dimensional coordination polymer resulting from the reaction of [Cu(MeCN)4][PF6] with 1,3-dithiolane. The cationic one-dimensional ribbon consists of two copper(I) centers each ligated by one acetonitrile molecule and interconnected through two bridging 1,3-dithiolane ligands. One S-donor site of each ligand is κ1-bound to Cu, whereas the second S atom acts as a four-electron donor, bridging two Cu atoms in a κ4-bonding mode. The positive charge of each copper cation is compensated for by a hexafluoridophosphate counter-ion. In the crystal, the polymer chains are linked by a series of C—H...F hydrogen bonds, forming a supramolecular framework.
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41

Ren, YiXin, Andrea M. Bruck et Lisa F. Szczepura. « Octa-μ3-selenido-pentakis(triethylphosphane-κP)(trimethylacetonitrile-κN)-octahedro-hexarhenium(III) bis(hexafluoridoantimonate) trimethylacetonitrile monosolvate ». Acta Crystallographica Section E Structure Reports Online 70, no 7 (4 juin 2014) : m242—m243. http://dx.doi.org/10.1107/s1600536814011982.

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The crystal structure of the title compound, [Re6Se8{NCC(CH3)3}(Et3P)5](SbF6)2·NCC(CH3)3, contains a face-capped octahedral [Re6(μ3-Se)8]2+cluster core. The pseudo-centrosymmetric [Re6Se8]2+cluster core is bonded through the Re atoms to five triethylphosphane ligands and one trimethylacetonitrile ligand. No significant interactions are observed between the cationic cluster, the SbF6−anions and the trimethylacetonitrile solvent molecule.
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42

Du, Bin, Si-Chun Yuan et Jian Pei. « Cationic Iridium Dendrimers : Synthesis and Photophysical Properties ». Australian Journal of Chemistry 64, no 9 (2011) : 1211. http://dx.doi.org/10.1071/ch11143.

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Two dendrimers, D1 and D2, containing the cationic iridium complexes (C1 and C2) as cores and truxene-functionalized chromophores as the branches, have been developed by a convergent synthetic strategy. The cationic complexes employ 3-(pyridin-2-yl)-1H-1,2,4-triazole and 2-(pyridin-2-yl)-benzimidazole derivatives as the ancillary ligands. To avoid the change in emission colour arising from the iridium complex, the conjugation between the dendron and the ligand is decoupled by separating them using the alkyl chain. An investigation of their photoluminescent features reveals that efficient energy transfer happens from the dendrons to the core in the solid state. Likewise, the charged dendritic structure is demonstrated to be an efficient method to improve the compatibility between the polar charged iridium complexes and typical hydrophobic hosts with the additional benefit of excellent solution processability. Both dendrimers exhibit strong solvatochromic behaviours in solvents and exclusive green and yellow-orange light in the solid state.
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43

Lee, Byungwoo, et Jung Hoon Song. « Surface Decomposition and Healing in Solution-Phase Ligand Exchange for Efficient Colloidal Quantum Dot Solar Cells ». Science of Advanced Materials 14, no 1 (1 janvier 2022) : 141–46. http://dx.doi.org/10.1166/sam.2022.4189.

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The efficiency of solution-processed colloidal quantum dot (CQD) thin-film solar cells has been significantly improved recently. However, there is still potential for efficiency improvements, which can be realized through a deeper understanding of surface chemical treatment for CQDs. In this study, we developed CQD thin-film solar cells with an improved power conversion efficiency (PCE) of 11.97%. We accomplished this by simply controlling the species and their molar concentrations used in the surface chemical treatment in the solutionphase ligand exchange process. Iodine treatment that generates conductive CQDs induces surface defects via cationic decomposition of the CQD surface; healing the CQD surface requires an excess of lead cations in the solution-phase ligand exchange process. Accordingly, we found that manufacturing CQD thin-film solar cells that have high efficiencies requires well-controlled surface treatment to effectively exchange surface ligands and simultaneously minimize surface defects on the CQD surface.
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44

MacBeth, Cora E., Seth B. Harkins et Jonas C. Peters. « Synthesis and characterization of cationic iron complexes supported by the neutral ligands NPi-Pr3, NArPi-Pr3, and NSt-Bu3 ». Canadian Journal of Chemistry 83, no 4 (1 avril 2005) : 332–40. http://dx.doi.org/10.1139/v05-017.

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This paper compares the local geometries, spin states, and redox properties of a series of iron complexes supported by neutral, tetradentate NP3 (tris(phosphine)amine) and NS3 (tris(thioether)amine) ligands. Our consideration of an Fe-mediated N2 fixation scheme similar to that proposed by Chatt for molybdenum motivates our interest in systems of these types. This report specifically describes the synthesis and characterization of cationic Fe(II) chloride complexes supported by the neutral ligands NPi-Pr3 (NPi-Pr3 = [N(CH2CH2P-i-Pr2)3]), NArPi-Pr3 (NArPi-Pr3 = [N(2-diisopropylphosphine-4-methylphenyl)3]), and NSt-Bu3 (NSt-Bu3 = [N(CH2CH2S-t-Bu)3]). The solid-state structures, electrochemistry, and magnetic properties of these complexes are reported. Whereas the NPi-Pr3 and NArPi-Pr3 ligands provide pseudotetrahedral S = 2 ferrous cations [Fe(NPi-Pr3)Cl]PF6 (1[PF6]) and [Fe(NArPi-Pr3)Cl]BPh4 (2[BPh4]) featuring a long Fe—N bond distance, the NSt-Bu3 ligand gives rise to a trigonal bipyramidal structure with a S = 1 ground state and a much shorter Fe–N interaction. The complexes 1[BPh4] and 2[BPh4] can be reduced under CO to give rise to the five-coordinate Fe(I) monocarbonyls [Fe(NPi-Pr3)CO]BPh4 (4[BPh4]) and [Fe(NArPi-Pr3)CO]BPh4 (5[BPh4]). The solid-state structures and electrochemistry of 4[BPh4] and 5[BPh4] are described, as is the EPR spectrum of 4[BPh4]. The synthesis and characterization of the hydride–dinitrogen complex [Fe(NPi-Pr3)(N2)(H)]PF6 (6[PF6]) has also been accomplished and its properties are also reported.Key words: nitrogenase, iron, polydentate phosphines, thioether ligands, N2 chemistry, nitrogen, Fe(I).
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45

Liu, Ruihuan, Dongxin Ma, Chen Zhang et Lian Duan. « Sublimable cationic iridium(iii) complexes with large steric hindrance for high-performance organic light-emitting diodes ». Dalton Transactions 48, no 26 (2019) : 9669–75. http://dx.doi.org/10.1039/c9dt00495e.

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46

Milocco, Francesca, Serhiy Demeshko, Franc Meyer et Edwin Otten. « Ferrate(ii) complexes with redox-active formazanate ligands ». Dalton Transactions 47, no 26 (2018) : 8817–23. http://dx.doi.org/10.1039/c8dt01597j.

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47

Battistin, Federica, Alessio Vidal, Gabriele Balducci et Enzo Alessio. « Investigating the reactivity of neutral water-soluble Ru(ii)–PTA carbonyls towards the model imine ligands pyridine and 2,2′-bipyridine ». RSC Advances 10, no 45 (2020) : 26717–27. http://dx.doi.org/10.1039/d0ra05898j.

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The reactivity of selected Ru(ii)-PTA carbonyls with potentially labile ligands (i.e. H2O, dmso and/or Cl) towards the model imine ligands pyridine and 2,2′-bipyridine was investigated, yielding several neutral and cationic water-soluble derivatives.
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48

Carballo, Rosa, Ana Belén Lago, Arantxa Pino-Cuevas, Olaya Gómez-Paz, Nuria Fernández-Hermida et Ezequiel M. Vázquez-López. « Neutral and Cationic Chelidonate Coordination Polymers with N,N′-Bridging Ligands ». Chemistry 3, no 1 (11 février 2021) : 256–68. http://dx.doi.org/10.3390/chemistry3010019.

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The biomolecule chelidonic acid (H2chel, 4-oxo-4H-pyran-2,6-dicarboxylic acid) has been used to build new coordination polymers with the bridging N,N′-ligands 4,4′-bipyridine (4,4-bipy) and 1,2-bis(4-pyridyl)ethane (bpe). Four compounds have been obtained as single crystals: 1D cationic coordination polymers [M(4,4-bipy)(OH2)4]2+ with chelidonate anions and water molecules in the second coordination sphere in 1∞[Zn(4,4-bipy)(H2O)4]chel·3H2O (2) and in the two pseudopolymorphic 1∞[Cu(4,4-bipy)(H2O)4]chel·nH2O (n = 3, 4a; n = 6, 4b), and the 2D neutral coordination polymers 2∞[Zn(chel)(4,4-bipy)(H2O)]·2H2O (1) and 2∞[Zn(chel)(bpe)(H2O)]·H2O (3) where the chelidonate anion acts as a bridging ligand. The effects of the hydrogen bonds on the crystal packing were analyzed. The role of the water molecules hosted within the crystals lattices was also studied.
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49

Cabeza, Javier A, Ignacio del Río, María C Goite, Enrique Pérez-Carreño et Vanessa Pruneda. « Cationic Heterocycles as Ligands : Synthesis and Reactivity with Anionic Nucleophiles of Cationic Triruthenium Clusters Containing C-MetalatedN-Methylquinoxalinium orN-Methylpyrazinium Ligands ». Chemistry - A European Journal 15, no 30 (27 juillet 2009) : 7339–49. http://dx.doi.org/10.1002/chem.200901079.

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50

Spiridonova, Yulia S., Yulia A. Nikolaeva, Anna S. Balueva, Elvira I. Musina, Igor A. Litvinov, Igor D. Strelnik, Vera V. Khrizanforova, Yulia G. Budnikova et Andrey A. Karasik. « Synthesis and Structure of Iron (II) Complexes of Functionalized 1,5-Diaza-3,7-Diphosphacyclooctanes ». Molecules 25, no 17 (19 août 2020) : 3775. http://dx.doi.org/10.3390/molecules25173775.

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In order to synthesize new iron (II) complexes of 1,5-diaza-3,7-diphosphacyclooctanes with a wider variety of the substituents on ligands heteroatoms (including functionalized ones, namely, pyridyl groups) and co-ligands, it was found that these ligands with relatively small phenyl, benzyl, and pyridin-2-yl substituents on phosphorus atoms in acetonitrile formed bis-P,P-chelate cis-complexes [L2Fe(CH3CN)2]2+ (BF4)2−, whereas P-mesityl-substituted ligand formed only monoligand P,P-complex [LFe(CH3CN)4]2+ (BF4)2−. 3,7-dibenzyl-1,5-di(1′-(R)-phenylethyl)-1,5-diaza-3,7-diphosphacyclooctane reacted with hexahydrate of iron (II) tetrafluoroborate in acetone to give an unusual bis-ligand cationic complex of the composition [L2Fe(BF4)]+ BF4−, where two fluorine atoms of the tetrafluoroborate unit occupied two pseudo-equatorial positions at roughly octahedral iron ion, according to X-ray diffraction data. 1,5-diaza-3,7-diphosphacyclooctanes replaced tetrahydrofurane and one of the carbonyl ligands of cyclopentadienyldicarbonyl(tetrahydrofuran)iron (II) tetrafluoroborate to form heteroligand complexes [CpFeL(CO)]+BF4−. The structural studies in the solid phase and in solutions showed that diazadiphosphacyclooctane ligands of all complexes adopted chair-boat conformations so that their nitrogen atoms were in close proximity to the central iron ion. The redox properties of the obtained complexes were performed by the cyclic voltammetry method.
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