Mössbauer and Infrared Spectra of Octahedral Complexes of Iron(II) Halides with Amides and Related Ligands

Birchall, T.; Morris, Michael

doi:10.1139/v72-030

Cited by 18 publications

(4 citation statements)

References 17 publications

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“…The major doublet (64%) has nuclear parameters that are characteristic of high-spin ( S = 2) Fe II (δ = 1.24 mm s –1 , Δ E Q = 2.07 mm s –1 ). The isomer shift value is in agreement with that previously determined for an analogous 1D chain . The second doublet (δ = 1.20 mm s –1 , Δ E Q = 1.34 mm s –1 , contribution 26%) also exhibits nuclear parameters featuring a high-spin Fe II ion.…”

Section: Resultsmentioning

confidence: 99%

“…The isomer shift value is in agreement with that previously determined for an analogous 1D chain. 22 The second doublet (δ = 1.20 mm s −1 , ΔE Q = 1.34 mm s −1 , contribution 26%) also exhibits nuclear parameters featuring a high-spin Fe II ion. The two species differ in the quadrupole splitting values, suggesting that the two molecules of acetonitrile may be in either the trans or cis positions.…”

Section: T1mentioning

confidence: 99%

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Elucidating Dramatic Ligand Effects on SET Processes: Iron Hydride versus Iron Borohydride Catalyzed Reductive Radical Cyclization of Unsaturated Organic Halides

et al. 2017

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International audienceAn iron(II) borohydride complex ([(η1-H3BH)FeCl(NCCH3)4]) is employed as the precatalyst in iron-catalyzed radical cyclizations of unsaturated organic halides in the presence of NaBH4. Mechanistic investigations have established that the ligand bound to the metal center (acetonitrile versus ethylenebis(diphenylphosphine) (dppe)) plays a crucial role in the structure and reactivity of the active anionic iron(I) hydride ([HFeCl(dppe)2]−) and borohydride ([(η1-H3BH)FeCl(NCCH3)4]−) with unsaturated haloacetals. This work provides new insights into iron(I) hydride and borohydride species and their potential implication in single-electron processes

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Section: Resultsmentioning

confidence: 99%

Section: T1mentioning

confidence: 99%

Elucidating Dramatic Ligand Effects on SET Processes: Iron Hydride versus Iron Borohydride Catalyzed Reductive Radical Cyclization of Unsaturated Organic Halides

et al. 2017

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“…The obtained values of C have been compared with the expected values for noninteracting spins. Using the value of S Fe = 2 and S Cu = 1/2 and published g-factors which are for Cu 2+ in an elongated octahedral environment between 2 and 2.1 52 and for Fe 2+ have an octahedral geometry, this value can be anywhere between 1.975 and 2.245, 53 for the Curie constant it follows 8.1(2) emu K mol −1 Oe −1 . We saw good agreement of this value with the experimentally determined points to the paramagnetic state of noninteracting spins in 4a and 4b at high temperatures.…”

Section: H J S S J S S S S G H S (mentioning

confidence: 99%

Structural, Electrical, and Magnetic Versatility of the Oxalate-Based [CuFe] Compounds Containing 2,2′:6′,2″-Terpyridine: Anion-Directed Synthesis

et al. 2020

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The heterodimetallic [CuFe] compounds [CuII 4(terpy)4Cl5][FeIII(C2O4)3]·10H2O (1;terpy = 2,2′:6′,2′′-terpyridine), [CuII 2(H2O)2(terpy)2(C2O4)][CuIIFeIII(CH3OH)(terpy)(C2O4)3]2 (2), and {[Cu2 IIFeIII(H2O)(terpy)2(C2O4)7/2]·6H2O} n (3) were obtained using building block approach, from reaction of aqueous solution of [Fe(C2O4)3]3– and a methanol solution containing Cu2+ ions and terpy by the layering technique. Interestingly, by changing only the anion of the starting salt of copper(II), Cu(NO3)2·3H2O instead of CuCl2·2H2O, an unexpected change in the type of bridge, oxalate (2 and 3) versus chloride (1), was achieved, thus affecting the overall structural architecture. Two polymorphs of 3D coordination polymer [CuIIFeII 2(H2O)(terpy)(C2O4)3] n (4), crystallizing in the triclinic (a) and monoclinic (b) space groups, were formed hydrothermally, depending on whether CuCl2·2H2O or Cu(NO3)2·3H2O was added to the water, besides K3[Fe(C2O4)3]·3H2O and terpy, respectively. Under hydrothermal conditions iron(III) from initial building block is reduced to the divalent state, creating 2D honeycomb [FeII 2(C2O4)3] n 2n– layers, which are bridged by [Cu(H2O)(terpy)]2+ cations. Compounds were investigated by single-crystal X-ray diffraction, IR, and impedance spectroscopies, magnetization measurements, and density functional theory (DFT) calculations. In compounds 1 and 2, 0D magnetism is observed, with 1 having a ground-state spin of 1 due to different interactions through chloride bridges of Cu2+ ions in tetramer [CuII 4(terpy)4Cl5]3+ and 2 showing strong antiferromagnetic coupling of Cu2+ ions mediated by oxalate ligand in [CuII 2(H2O)2(terpy)2(C2O4)]2+ and weak ones between Cu2+ and Fe3+ ions through oxalate bridge in [CuIIFeIII(CH3OH)(terpy)(C2O4)3]−. Polymer 4 exhibits antiferromagnetic phase transition at 25 K: The [FeII 2(C2O4)3] n 2n– layers are antiferromagnetically ordered, and a small amount of interlayer interaction is transferred through [Cu(H2O)(terpy)]2+ cations via Oox–Cu–Oox bridges. Additionally, compounds 1 and 2 are electrical insulators, while 4a and 4b show proton conductivity.

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“…In some cases, the Mossbauer results provide the primary evidence for a presumed structure. Thus, IR, Mossbauer, and magnetic moments were studied for ferrous halide complexes by Birchall and Morris (67,68). The Mossbauer results distinguished between tetrahedral and octahedral complexes and between polymeric and monomeric structures for a variety of amide and thioamide ligands.…”

Section: Routine Usagementioning

confidence: 99%

Moessbauer spectrometry

Stevens¹,

Bowen²

1974

Anal. Chem.

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is an associate professor of chemistry at the University of North Carolina at Asheville. He received his B.S, (1964) degree in chemistry and Ph.D. (1969) in physical chemistry from North Carolina State University. He has spent three summers at Argonne National Laboratory and this past fall was on a leave of absence at Max-Planck-Institut Für Festkorperforschung. His main research interest is Mossbauer spectrometry and its application to the study of antimony compounds, frozen solutions, minerals, and substances under high pressure. He coedits the "Mossbauer Effect Data Index" with V. E. Stevens. He served on the Ad Hoc Panel on Mossbauer Data Evaluation of the National Academy of Sciences. He is a member of ACS,

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Mössbauer and Infrared Spectra of Octahedral Complexes of Iron(II) Halides with Amides and Related Ligands

Cited by 18 publications

References 17 publications

Elucidating Dramatic Ligand Effects on SET Processes: Iron Hydride versus Iron Borohydride Catalyzed Reductive Radical Cyclization of Unsaturated Organic Halides

Elucidating Dramatic Ligand Effects on SET Processes: Iron Hydride versus Iron Borohydride Catalyzed Reductive Radical Cyclization of Unsaturated Organic Halides

Structural, Electrical, and Magnetic Versatility of the Oxalate-Based [CuFe] Compounds Containing 2,2′:6′,2″-Terpyridine: Anion-Directed Synthesis

Moessbauer spectrometry

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