The spin state crossover in ferric pyrrolidyl dithiocarbamate, and the effect of nitrobenzene in inducing lowering of spin states

doi:10.1016/0020-1650(77)80044-5

Inorganic and Nuclear Chemistry Letters

Volume 13, Issue 7, 1977, Pages 283-286

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Cited by (16)

The anomalous Mössbauer spectra of tris(diethanoldithiocarbamato)iron(III): Solvate effects
1992, Inorganica Chimica Acta
Attempts to repeat the previously reported preparation of Fe(S₂CN(CH₂CH₂OH)₂)₃·3H₂O from aqueous solution always yielded the unsolvated complex which displayed a normal two-line MÖssbauer spectrum similar to those displayed by Fe(S₂CN(CH₂CH₂OH)₂)₃ prepared in non-aqueous media. Contrary to previous reports, heating the sample did not produce an unsolvated sample, but instead, resulted in decomposition as indicated by elemental analysis, TGA and MÖssbauer studies. In contrast to earlier reports, Fe(S₂CN(CH₂CH₂OH)₂)₃ was successfully recrystallized from acetone and methanol. Each of these recrystallized complexes was, for the most part, quite ordinary in its elemental analysis, room-temperature magnetic moment (predominantly high spin) and Mössbauer spectrum. However, when Fe(S₂CN(CH₂CH₂OH)₂)₃ prepared from ethanolic solution is recrystallized from methanol without heating during the removal of the methanol, the resulting complex yields a four-line Mössbauer spectrum at 77 K (isomer shifts: 0.726, 0.770 mm/s; quadrupole splittings: 1.18, 0.318 mm/s, respectively). The elemental analysis, room-temperature magnetic moment and EPR spectra of this complex were in accord with a predominantly high-spin, spin-crossover complex without sufficient solvate molecules to be detectable by elemental analysis. A detailed, temperature-dependent series of Mössbauer spectra are reported for this complex. These results are discussed on the basis of effects of small amounts of solvate molecules on the spin-crossover rate of these complexes and compared to reports of four-line Mössbauer spectra for Fe(S₂CN(CH₂)₄O)₃·CH₂Cl₂ at 77 K.
Mössbauer spectra of tris(diorganothioselenocarbamato)- and tris(diorganodiselenocarbamato)iron(III) complexes
1990, Inorganica Chimica Acta
Room temperature ⁵⁷Fe Mössbauer spectra of several tris(diorganothioselenocarbamato)- and tris(diorganodiselenocarbamato)iron(III) complexes are reported, along with their room temperature magnetic moments for the solid state. These results are compared to the previously reported diethyl derivatives and to the corresponding monothio- and dithiocarbamates. Each complex exhibited a single, quadrupole-split absorption in its Mössbauer spectrum. Although variations are noted within specific organic substituents, general trends for the average isomer shifts of all ligands are ⁻OSCNR₂ < ⁻S₂CNR₂ ∼⁻SSeCNR₂ ∼⁻Se₂CNR₂, while the typical order of the quadrupole splittings for a given ligand is ⁻OSCNR₂ < ⁻S₂CNR₂ < ⁻SSeCNR₂ < ⁻Se₂CNR₂. For the same organic substituent, the magnetic moments usually decrease in the order ⁻OSCNR₂ > ⁻S₂CNR₂ > ⁻SSeCNR₂ > ⁻Se₂CNR₂.
It is noteworthy that higher quadrupole splittings are observed for the symmetric diselenocarbamate iron(III) complexes than for the corresponding thioselenocarbamates.
Compounds with intermediate spin. 9. Crystal structure of a novel tris(4-morpholinecarbodithiato)iron(III)- dichloromathane phase. Correlation between structural and magnetic properties in tris(4-morpholinecarbodithiato)iron(III) solvates
1983, Inorganica Chimica Acta
The crystal structure of Fe(S₂CNC₄H₈O)₃·CH₂Cl₂ phase III, M_r = 627.11, Has been determined with direct and Fourier methode from X-ray four-circle single-crystal diffractometer data at 293 K. The space group is triclinic, P $1$ , with Z = 2; a = 9.264(1) Å; b = 10.459(1) Å; c = 13.665(2) Å; α = 100.65(1)°; β = 95.60(1)°; γ = 105.83(1)°; V = 1236(1) Å³; D_x = 1.684 g cm(−3). The refinement converged to R = 0.028. The effective magnetic moment was determined using the Faraday method and is constant at 5.9 B.M. between 77 and 320 K. The complexes are mononuclear with pseudosymmetry D₃ and the van der Waals packed together with disordered dichloromethane molecules. The geometry of the complexes is that expected from a high spin tris(dithiocarbomato) iron(III) compound. The effective magnetic moments of tris(4-morpholinecarbodithiato)iron(III) solvates are found to be strongly correlated to the deformation of the central CN in the ligands. Increased deformation decreases the π-bond overlap and favours the low spin canonical form of the ligand. Non-polar solvents crystallizes around the non-polar morphine ring of the ligand resulting in a stronger deformation of the ligand than for the polar solvents crystallizing preferably near the FeS₆ core of the complex.
Six coordinate iron(III), the S = 3 2 ground state and particle size
1981, Inorganic and Nuclear Chemistry Letters
EPR studies of spin-crossover of the tris-(di-n-butyldithiocarbamato)Fe(III) chlorobenzene solvate
1980, Journal of Inorganic and Nuclear Chemistry
EPR studies of tris-(di-n-butyldithiocarbamato)Fe(III), with and without a chlorobenzene solvate, were performed from −160°C to room temperature. A line at an approximate g-value of 4.4 was assigned as a $S = 52$ line and its temperature dependent behavior was correlated with solid magnetic moment observations. An additional narrower line was noted in the spectrum of the solvated sample. We associate this line with a second possible high-energy site for the chlorobenzene solvate molecule. A solvate molecule in this site appears to “shut off” the spin-crossover.
The dependence of Mössbauer isomer shifts on magnetic moments in solvated tris-dithiocarbamates on iron(III)
1980, Journal of Inorganic and Nuclear Chemistry

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Inorganic and Nuclear Chemistry Letters

The spin state crossover in ferric pyrrolidyl dithiocarbamate, and the effect of nitrobenzene in inducing lowering of spin states

First page preview

Bull. Amer. Phys. Soc.

Bull. Amer. Phys. Soc.

Inorg. Chem.

J. Amer. Chem. Soc.

J. Amer. Chem. Soc.

J. Chem. Soc. Chem. Comm.

Aust. J. Chem.

The anomalous Mössbauer spectra of tris(diethanoldithiocarbamato)iron(III): Solvate effects

Mössbauer spectra of tris(diorganothioselenocarbamato)- and tris(diorganodiselenocarbamato)iron(III) complexes

Compounds with intermediate spin. 9. Crystal structure of a novel tris(4-morpholinecarbodithiato)iron(III)- dichloromathane phase. Correlation between structural and magnetic properties in tris(4-morpholinecarbodithiato)iron(III) solvates

Six coordinate iron(III), the S = 3 2 ground state and particle size

EPR studies of spin-crossover of the tris-(di-n-butyldithiocarbamato)Fe(III) chlorobenzene solvate

The dependence of Mössbauer isomer shifts on magnetic moments in solvated tris-dithiocarbamates on iron(III)