Transition metal complexes with thiosemicarbazide-based ligands. 14. Iron(IV) complexes with 2,4-pentanedione bis(S-alkylisothiosemicarbazone). Crystal and molecular structure of iodo{2,4-pentanedione bis(S-ethylisothiosemicarbazonato)(3-)}iron(IV)

Gérbéléu, N. V.; Simonov, Yu. A.; Arion, V. B.; Leovac, Vukadin M.; Turta, K. I.; Indrichan, K. M.; Gradinaru, D.I.; Zavodnik, V. E.; Malinovskii, T. I.

doi:10.1021/ic00041a019

Cited by 48 publications

(19 citation statements)

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“…3a) is close to the spin-only value for two unpaired electrons (2.83 μ B ) and clearly shows the intermediate spin state of iron(IV) in this complex25354546. Above 40 K, the value of μ eff is nearly temperature independent, whereas below this temperature μ eff decreases steeply because of zero-field splitting.…”

Section: Resultssupporting

confidence: 69%

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

et al. 2017

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In nature, iron, the fourth most abundant element of the Earth's crust, occurs in its stable forms either as the native metal or in its compounds in the +2 or +3 (low-valent) oxidation states. High-valent iron (+4, +5, +6) compounds are not formed spontaneously at ambient conditions, and the ones obtained synthetically appear to be unstable in polar organic solvents, especially aqueous solutions, and this is what limits their studies and use. Here we describe unprecedented iron(IV) hexahydrazide clathrochelate complexes that are assembled in alkaline aqueous media from iron(III) salts, oxalodihydrazide and formaldehyde in the course of a metal-templated reaction accompanied by air oxidation. The complexes can exist indefinitely at ambient conditions without any sign of decomposition in water, nonaqueous solutions and in the solid state. We anticipate that our findings may open a way to aqueous solution and polynuclear high-valent iron chemistry that remains underexplored and presents an important challenge.

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Section: Resultssupporting

confidence: 69%

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

et al. 2017

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“…It has also been proposed that in diamagnetic, octahedral [Fe(CN) 2 (${{\rm L}{{{\rm Ox}\hfill \atop {\rm TSC}\hfill}}}$ )] − ( 14 ) a low‐spin Fe II ion (d 6 ; S =0) is present21 and a monoanionic, diamagnetic ligand (${{\rm L}{{{\rm Ox}\hfill \atop {\rm TSC}\hfill}}}$ ) − (Scheme ). Again the reported experimental Mössbauer parameters are apparently in accord with this interpretation 20. 21 For both complexes there exist alternative descriptions of their electronic structures if one takes into account the possibility that the ligand can actually be a dianionic π radical, (L .…”

Section: Resultsmentioning

confidence: 69%

“…Complexes containing pentane‐2,4‐dione‐bis( S ‐alkylisothiosemicarbazonato) n ligands ( n =3−, 2−, 1−) : Gerbeleu et al 20. and Wieghardt et al 21.…”

Section: Resultsmentioning

confidence: 99%

Electronic Structures of Five‐Coordinate Complexes of Iron Containing Zero, One, or Two π‐Radical Ligands: A Broken‐Symmetry Density Functional Theoretical Study

Chłopek

Muresan

Neese

et al. 2007

Chemistry A European J

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The electronic structures of a series of five-coordinate complexes of iron containing zero, one, or two bidentate, organic pi-radical ligands and a monodentate ligand (pyridine, iodide) have been studied by broken-symmetry (BS) density functional theoretical (DFT) methods. By analyzing the set of corresponding orbitals[5] (CO) a convenient division of the spin-up and spin-down orbitals into 1) essentially doubly-occupied molecular orbitals (MO), 2) exactly singly-occupied MOs, 3) spin-coupled pairs, and 4) virtual orbitals can be achieved and a clear picture of the spin coupling between the ligands (non-innocence vs. innocence) and the central metal ion (dN configuration) can be generated. We have identified three classes of complexes which all contain a ferric ion (d5) with an intrinsic intermediate spin (SFe= 3/2) that yield 1) an St=3/2 ground spin state if the two bidentate ligands are closed-shell species (innocent ligands); 2) if one pi-radical ligand is present, an St=1 ground state is obtained through intramolecular antiferromagnetic coupling; 3) if two such radicals are present, an St=1/2 ground state is obtained. We show unambiguously for the first time that the pentane-2,4-dione-bis(S-alkylisothiosemicarbazonato) ligand can bind as pi-radical dianion (L.TSC)2- in [FeIII(L.TSC)I] (St=1) (6); the description as [Fe IV(L TSC(3-))I] is incorrect. Similarly, the diamagnetic monoanion in 14 must be described as [FeIII(CN)2(L.TSC)](-) (St=0) with a low-spin ferric ion (d5, SFe=1/2) coupled antiferromagnetically to a pi-radical ligand; [FeII(CN)2(L TSC-]- is an incorrect description.

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“…[4][5][6][7][8][9][10][11]; they can be used as potential MRI contrast agents [12] and fluorescent sensors [13,14]. Semicarbazide is able to coordinate metal ions [15][16][17][18][19][20][21][22][23][24] and the biological activities of these complexes are associated with the formation of chelates with various metal ions, bonding through N or O donors. Semicarbazides and their metal complexes attract considerable attention because they have applications in medicine as lathyrogenic and teratogenic agents [25].…”

Section: Introductionmentioning

confidence: 99%

Cobalt(II), nickel(II), and copper(II) complexes of 14-membered hexaazamacrocycles: synthesis and characterization

Volov

Zamilatskov

Чернышев

et al. 2014

Journal of Coordination Chemistry

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Cobalt(II), nickel(II), and copper(II) complexes containing 5,12-di(4-bromophenyl)-7, 14-dimethyl-1,2,4,8,9,11-hexaazacyclotetradeca-7,14-diene-3,10-dione (H 2 L 1 ) and 5,12-diphenyl-7,14-dimethyl-1,2,4,8,9,11-hexaazacyclotetradeca-7,14-diene-3,10-dione (H 2 L 2 ) have been synthesized. All complexes were characterized by elemental analysis, MALDI TOF-MS spectrometry, and electronic absorption spectroscopy. The crystal structures of two compounds, [Cu 2 (H 2 L 1 )Cl 4 ] n and [NiL 2 ], were determined by X-ray powder diffraction. In the polymeric [Cu 2 (H 2 L 1 )Cl 4 ] n , the Cu 2 Cl 4 units and H 2 L 1 molecules are situated on inversion centers. Each Cu(II) has a distorted trigonal-bipyramidal coordination environment formed by N and O from H 2 L 1 [Cu-N 2.340(14) Å, Cu-O 1.952(11) Å], two bridging chlorides [Cu-Cl 2.332(5), 2.279(5) Å] and one terminal chloride [Cu-Cl 2.320(6) Å]. In the [NiL 2 ] complex, the Ni(II) situated on inversion center has a distorted square-planar coordination environment formed by four nitrogens from L 2 [Ni-N 1.860(11), 1.900(11) Å].

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Transition metal complexes with thiosemicarbazide-based ligands. 14. Iron(IV) complexes with 2,4-pentanedione bis(S-alkylisothiosemicarbazone). Crystal and molecular structure of iodo{2,4-pentanedione bis(S-ethylisothiosemicarbazonato)(3-)}iron(IV)

Cited by 48 publications

References 0 publications

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

Indefinitely stable iron(IV) cage complexes formed in water by air oxidation

Electronic Structures of Five‐Coordinate Complexes of Iron Containing Zero, One, or Two π‐Radical Ligands: A Broken‐Symmetry Density Functional Theoretical Study

Cobalt(II), nickel(II), and copper(II) complexes of 14-membered hexaazamacrocycles: synthesis and characterization

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