An unusual diverse coordination of silver(I) with N-allylthiohydantoin ligand in the presence of benzene- and p-toluenesulfonate anions

Fedorchuk, A. A.; Slyvka, Yu. I.; Kinzhybalo, Vasyl; Lis, Tadeusz; Mys’kiv, М. G.

doi:10.1016/j.ica.2018.09.029

Cited by 6 publications

(7 citation statements)

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“…The copper(I) ions in 3 and 4 as well as the silver ions in 5 , 6a , and 6b are coordinated in a distorted disphenoidal geometry (seesaw geometry) by both oxygen (equatorial) and nitrogen (axial) atoms of the ligands. This seesaw coordination is very rare for copper(I) complexes, less so for silver(I). − There are no hydrogen atoms in proximity suitable to complete a possible trigonal bipyramidal or even octahedral geometry around the metal, either via agostic or conventional H-bonding to the metal(I) center. The closest atom in proximity to Cu(I) in 3 is the fluorine atom of BF 4 – with a Cu···F distance of 4.061(2) Å; in 4 , it is the fluorine atom of PF 6 – with a Cu···F distance of 4.325(5) Å.…”

Section: Resultsmentioning

confidence: 99%

Investigation of Structural Changes of Cu(I) and Ag(I) Complexes Utilizing a Flexible, Yet Sterically Demanding Multidentate Phosphine Oxide Ligand

et al. 2021

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The syntheses of a sterically demanding, multidentate bis(quinaldinyl)phenylphosphine oxide ligand and some Cu(I) and Ag(I) complexes thereof are described. By introducing a methylene group between the quinoline unit and phosphorus, the phosphine oxide ligand gains additional flexibility. This specific ligand design induces not only a versatile coordination chemistry but also a rarely observed and investigated behavior in solution. The flexibility of the birdlike ligand offers the unexpected opportunity of open-wing and closed-wing coordination to the metal. In fact, the determined crystal structures of these complexes show both orientations. Investigations of the ligand in solution show a strong dependency of the chemical shift of the CH 2 protons on the solvent used. Variable-temperature, multinuclear NMR spectroscopy was carried out, and an interesting dynamic behavior of the complexes is observed. Due to the introduced flexibility, the quinaldinyl substituents change their arrangements from open-wing to closed-wing upon cooling, while still staying coordinated to the metal. This change in conformation is completely reversible when warming up the sample. Based on 2D NMR spectra measured at −80 °C, an assignment of the signals corresponding to the different arrangements was possible. Additionally, the copper(I) complex shows reversible redox activity in solution. The combination of structural flexibility of a multidentate ligand and the positive redox properties of the resulting complexes comprises key factors for a possible application of such compounds in transition-metal catalysis. Via a reorganization of the ligand, occurring transition states could be stabilized, and selectivity might be enhanced.

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Section: Resultsmentioning

confidence: 99%

Investigation of Structural Changes of Cu(I) and Ag(I) Complexes Utilizing a Flexible, Yet Sterically Demanding Multidentate Phosphine Oxide Ligand

et al. 2021

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“…Ligand Hath was synthesized from allylisothiocyanate and glycine at the presence of triethylamine and pyridine, in accordance with the reported method. 16…”

Section: Preparation Of 3-allyl-2thioxoimidazolidin-4-one (Hath)mentioning

confidence: 99%

“…In 16,17 In the first two coordination compounds, a complex coordination chain is formed, within which there are three crystallographically independent Ag(I) atoms with different coordination environments (tetragonal pyramidal, seesaw and distorted octahedral), four crystallographically independent molecules of Hath ligand and two anions of benzene-or toluenesulfonate. The Hath molecule is coordinated exclusively through the S atom of the thiogroup, which is bonded to several metal centers simultaneously.…”

Section: Atoms Involved Distances å Angle Deg D−h•••a D•••h H•••a D•••a D−h•••amentioning

confidence: 99%

“…[11][12][13][14][15] This work is the continuation of our previous studies, in which we have studied the coordination behavior of 3-allyl-2-thiohydantoin (Hath) regarding Ag(I), where obtained coordination compounds have already shown interesting structural peculiarities, confirming the status of 2-thiohydantoin-based molecules as the potential ligands in the structural engineering. 16,17…”

Section: Introductionmentioning

confidence: 99%

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Cu(I) Arylsulfonate π-Complexes with 3-Allyl-2-thiohydantoin: The Role of the Weak Interactions in Structural Organization

Fedorchuk

Goreshnik

Slyvka

et al. 2020

ACSi

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The present work is directed toward preparation and structural characterization of two novel Cu(I) arylsulfonate π-complexes with 3-allyl-2-thiohydantoin, namely [Cu2(Hath)4](C6H5SO3)2 (1) and [Cu2(Hath)4](p-CH3C6H4SO3)2 · 2H2O (2) (Hath = 3-allyl-2-thiohydantoin), obtained by the means of alternating current electrochemical synthesis and studied with X-ray diffraction method. In both structures, the inner coordination sphere is represented by the cationic dimer [Cu2(Hath)4]2+ with one crystallographically independent copper(I) atom which has a trigonal pyramidal coordination environment formed by three Hath thiogroup S atoms and double C=C bond of its allyl group. [Cu2(Hath)4]2+ fragments in both coordination compounds are very similar, despite some divergences such as a big difference in Cu−S distance to the apical S atom (3.0374(8) Å in 1 and 2.7205(9) Å in 2). This difference was explained by the impact of the system of weak interactions, which are quite different.

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“…All these different electron-donating atoms make 3-[(2-hydroxybenzylidene)amino]-2-thioxoimidazolidin-4-one an interesting chelating ligand towards metal ions. Some complexes with transition metal ions are already prepared, such as Ag(I) 27 , Hg(II) 28 , Co(II) 29.30 , Ni(II) 29,30 and Cu(II) [29][30][31] .…”

Section: O N L I N E F I R S Tmentioning

confidence: 99%

Reaction of a 3-aryilidene-2-thiohydantoin derivative with polymeric trans-[CuCl2(DMSO)2]n complex: Unexpected isomerization to dinuclear cis-[{CuCl(DMSO)2}(μ-Cl)]2

Stanić

Rodić

Soldatovic

et al. 2020

JSCS

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The 3-arylidene-2-thiohydantoin derivative, 3-[(2-hydroxybenzyl-idene)amino]-2-thioxoimidazolidin-4-one, was synthesized in a two-step condensation reaction of 2-hydroxybenzaldehyde, thiosemicarbazide and ethyl chloroacetate. The ligand was structurally characterized by NMR and IR spectroscopy, as well as elemental analysis. In the reaction of the well-known polymeric trans-[CuCl2(DMSO)2]n complex with the polydentate thiohydantoin type ligand, instead of the corresponding copper thiohydantoin complex, unexpectedly, the dinuclear cis-[{CuCl(DMSO)2}(m-Cl)]2 complex (1) was formed predominantly as the final stable product. The structure of the complex 1 was confirmed by single crystal X-ray diffraction analysis. The cis-complex is obtained through assisted isomerization of the trans-form, in which the thiohydantoin derivative has a crucial role. [Projects of the Serbian Ministry of Education, Science and Technological Development, Grant no. 451-03-68/2020-14/200378 and Grant no. 451-03-68/2020-14/200122]

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An unusual diverse coordination of silver(I) with N-allylthiohydantoin ligand in the presence of benzene- and p-toluenesulfonate anions

Cited by 6 publications

References 35 publications

Investigation of Structural Changes of Cu(I) and Ag(I) Complexes Utilizing a Flexible, Yet Sterically Demanding Multidentate Phosphine Oxide Ligand

Investigation of Structural Changes of Cu(I) and Ag(I) Complexes Utilizing a Flexible, Yet Sterically Demanding Multidentate Phosphine Oxide Ligand

Cu(I) Arylsulfonate π-Complexes with 3-Allyl-2-thiohydantoin: The Role of the Weak Interactions in Structural Organization

Reaction of a 3-aryilidene-2-thiohydantoin derivative with polymeric trans-[CuCl2(DMSO)2]n complex: Unexpected isomerization to dinuclear cis-[{CuCl(DMSO)2}(μ-Cl)]2

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