Magnetic and spectral properties of [Fe(en)3]Cl3

Renovitch, Gordon A.; Baker, W. A.

doi:10.1021/ja01015a064

Cited by 32 publications

(8 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The vis spectrum of the Fe III complex 3 in H 2 O showed maxima at 349 nm (ε = 211 M -1 cm -1 ), 408 nm (shoulder, ε = 56 M -1 cm -1 ), 441 nm (ε = 50 M -1 cm -1 ), and 522 nm (shoulder, ε = 21 M -1 cm -1 ). The effective magnetic moment μ eff increased monotonically from 1.98 μ B (3 K) to 2.78 μ B (300 K) displaying a significant orbital contribution at 300 K. All these spectroscopic and magnetic properties are in close agreement with those reported for other low-spin Fe III hexaamine complexes …”

Section: Resultssupporting

confidence: 86%

“…However, the rapid decomposition at high pH indicates that the high resistance towards hydrolysis in neutral solution has a kinetic rather than a thermodynamic origin. This is in contrast to [Fe(en) 3 ] 3+ which appears to be rather labile . Analogous reactivity differences have been observed between [Ni(en) 3 ] 2+ and [Ni(tach) 2 ] 2+ (tach = all- cis -1,3,5-triaminocyclohexane). , These can be attributed to the requirement for the cyclohexane ring to convert to the unfavorable boat conformation after dissociation of the first amine donor.…”

Section: Discussionmentioning

confidence: 76%

See 1 more Smart Citation

Selective Blocking of Coordination Modes in 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol: Enforced Formation of a Low-Spin Iron(III) Hexaamine Complex

et al. 1997

View full text Add to dashboard Cite

[Fe(tmca)2]3+ and [Co(tmca)2]3+ (tmca = all-cis-2,4,6-trimethoxycyclohexane-1,3,5-triamine) were prepared and characterized by elemental analyses, NMR, and FAB+ mass spectrometry and by spectroscopic methods (UV−vis). Magnetic susceptibility measurements established a low-spin d5 electron configuration for the FeIII hexaamine complex. In aqueous solution, cyclic voltammetry revealed a quasi reversible one electron reduction for both complexes with MIII/MII redox potentials of +0.16 and −0.30 V (vs SHE), respectively. The two compounds [M(tmca)2]Cl3·5H2O·EtOH (C20H58Cl3MN6O12, M = Fe, Co) are isostructural. They both crystallize in the triclinic space group P1̄, Z = 2. Fe complex: a = 10.338(3) Å, b = 13.062(4) Å, c = 14.042(4) Å, α = 80.20(2)°, β = 72.07(2)°, γ = 69.11(2)°. Co complex: a = 10.307(3) Å, b = 13.066(2) Å, c = 14.029(2) Å, α = 80.14(1)°, β = 72.18(2)°, γ = 69.55(2)°. The ligand tmca is compared with the unsubstituted 1,3,5-triamino-1,3,5-trideoxy-cis-inositol (taci) and the N-methylated 1,3,5-trideoxy-1,3,5-tris(dimethylamino)-cis-inositol (tdci). Due to the methyl groups on the oxygen donors, tmca binds both FeIII and CoIII ions exclusively via nitrogen donors whereas the previously reported [Fe(tdci)2]3+ had an FeO6 coordination environment. Equilibration of a 1:1 mixture of [Fe(tdci)2]3+ and [Fe(tmca)2]3+ in aqueous solution resulted in the quantitative formation of the metathesis product [Fe(tmca)(tdci)]Cl3·15H2O (O3N3 coordination). Crystal data: C21H78Cl3FeN6O21, trigonal, space group R3c, a = 15.158(2) Å, c = 33.591(7) Å, Z = 6. The differences in the structural properties of the low-spin hexaamine [Fe(tmca)2]3+ complex and the high-spin [Fe(tdci)2]3+ and [Fe(tmca)(tdci)]3+ complexes are discussed.

show abstract

Section: Resultssupporting

confidence: 86%

Section: Discussionmentioning

confidence: 76%

Selective Blocking of Coordination Modes in 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol: Enforced Formation of a Low-Spin Iron(III) Hexaamine Complex

et al. 1997

View full text Add to dashboard Cite

show abstract

“…Similar data have been obtained for low-spin complexes, many of which contain the same or similar ligands as those discussed in the high-spin examples but with more of the coordination positions being occupied by nitrogen donors to give the required increase in ligand field splitting [13,42,[49][50][51][52][53][54]. Similar data have been obtained for low-spin complexes, many of which contain the same or similar ligands as those discussed in the high-spin examples but with more of the coordination positions being occupied by nitrogen donors to give the required increase in ligand field splitting [13,42,[49][50][51][52][53][54].…”

Section: Chelating Ligandssupporting

confidence: 63%

Low-spin Iron(II) and Iron(III) Complexes

Greenwood

Gibb

1971

Mössbauer Spectroscopy

View full text Add to dashboard Cite

It was seen in the preceding chapter that the differing electronic configurations of iron(II) and iron(III) in high-spin complexes caused substantial and characteristic differences in the chemical isomer shift, quadrupole splitting, and magnetic field parameters of their Mossbauer spectra. The corresponding strong-ligand-field or low-spin complexes have 1 A 1g and 2T2g configurations under octahedral symmetry. The low-spin iron(II) 1 A 1 g{t2g 6) configuration has no unpaired electrons and is diamagnetic, whereas low-spin iron(III) 2T2 it2/) embodies an 'electron hole' in the t2g manifold and is paramagnetic, although magnetic ordering is sometimes observed at very low temperatures.The increased involvement of the iron 4s-orbitals in covalent bonding with the ligands, and the n-acceptor properties of ligands such as CN-combine to increase the s-electron density at the iron nucleus, and the observed chemical isomer shifts are therefore less positive than for the high-spin complexes (see Fig. 5.2). The difference in chemical isomer shift between low-spin iron(II) and iron(III) is also much less marked than between highspin iron(II) and iron(III) and this reduces the diagnostic usefulness of this parameter; however, the temperature dependence of the quadrupole splitting is a more reliable criterion of oxidation state. As seen in Chapter 5, the 2T2g configuration of Fe(III) shows appreciable thermal population of close-lying excited electronic levels when slightly distorted and thus has a strong temperature dependence of the quadrupole splitting whereas the lA lg configuration of Fe(II), having no intrinsic valence contribution to the electric field gradient, shows only a temperature-independent quadrupole splitting from the lattice terms.The comparative lack of magnetic exchange behaviour reduces the amount of information available from the Mossbauer spectra, and since the differences between the oxidation states are less marked, it is convenient to consider both in parallel.

show abstract

“…Previously, a tris-ethylenediaminenickel(II) complex has been reported (Swink & Atoji, 1960). Since then, such tris-ethylenediamine complexes have been reported for nearly all of the first row transition metals as well: scandium(III) (Wagner & Melson, 1973), titanium(II) (McDonald et al, 1968), vanadium(II) (Daniels et al, 1995), and vanadium(III) (Clark & Greenfield, 1967), chromium(III) (Whuler et al, 1975), iron(II) (Girard et al, 1998), iron(III) (Renovitch & Baker, 1968), cobalt(III) (Nakatsu, 1962), copper(II) (Cullen & Lingafelter, 1970) and zinc(II) (Emsley et al, 1989). Substituted tris-ethylenediamine complexes with methyl groups instead of hydrogen atoms bonded to the nitrogen atoms have not been reported, to the best of our knowledge.…”

Section: Structure Descriptionmentioning

confidence: 97%

trans-Diaquabis(N,N,N′-trimethylethylenediamine)nickel(II) dichloride

et al. 2020

View full text Add to dashboard Cite

In the title salt, [Ni(C5H12N2)2(H2O)2]Cl2, the asymmetric unit is comprised of half of the complex cation and a chloride ion with the NiII atom of the cation situated about a twofold rotation axis. The six-coordinate NiII atom of the cation is connected to four N atoms from two methyl-substituted ethyelenediamine ligands and two water molecules in a slightly distorted octahedral environment. The five-membered chelate ring is in a slight envelope conformation. The crystal packing features O—H...Cl and N—H...Cl intermolecular interactions with the Cl− ion forming weak bifurcated hydrogen bonds with nearby water molecules and N—H interactions, leading to a three-dimensional supramolecular network structure.

show abstract

Magnetic and spectral properties of [Fe(en)3]Cl3

Cited by 32 publications

References 0 publications

Selective Blocking of Coordination Modes in 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol: Enforced Formation of a Low-Spin Iron(III) Hexaamine Complex

Selective Blocking of Coordination Modes in 1,3,5-Triamino-1,3,5-trideoxy-cis-inositol: Enforced Formation of a Low-Spin Iron(III) Hexaamine Complex

Low-spin Iron(II) and Iron(III) Complexes

trans-Diaquabis(N,N,N′-trimethylethylenediamine)nickel(II) dichloride

Contact Info

Product

Resources

About