Table 3. Quadrupole splitting, ΔEQ and isomer shift, δ, for some iron compounds.

( ΔEQ and δ are in cms-1).

Compound ΔEQ δ Compound ΔEQ δ
2+ 3+
Spin-free Fe Spin-free Fe
FeSO4( Anhydrous) 0.270 0.120 FeCl3 (Anhydrous) 0.02 0.05
FeSO4.7H2O 0..315-0.320 0.130-0.119 FeCl3.6H2O 0.02 0.085
Fe(NH4)2(SO4)2. 6H2O 0.175 0.119 Fe(NO3)3.9H2O 0.04 0.04
FeC2O4. 2H2O 0.170 0.125 Fe2(C2O4)3 0.05 0.045
FeC4H4O6 0.260 0.125 Fe2(C4H4O6)3 0.077 0.043
FeCl2. 4H2O 0.300 0.135 Fe2O3 0.012 ---
Spin-paired Fe(II) Spin-paired Fe(III)
K4Fe(CN)6. 3H2O <0.01 +0.005 K3[Fe(CN)6] --- -0.012
K2 [Fe(CN)5NO] 0.185 -0.027 --- -0.017
Zn [Fe(CN)5NO] 0.190 -0.027 0.026 -0.015
Na4[Fe(CN)5.NH3] 0.06 -0.005 Na3[Fe(CN)6] 0.060 -0.017

In general, more positive shifts are obtained for bonded complexes and negative shifts for
extensive π-bonded complexes. In case of some ligands, the π-bonding tendencies have been
found to decrease in the following order :

NO+ > CO>CN- >SO2-3 > P (C6H5)3> NO3- >NH3.

The spectrum of the compounds obtained from Fe(III) SO4 and K4Fe(CN)6 is identical to the
spectra of the compounds prepared from either Fe(II) SO4 and K3Fe(CN)6 or by oxidation of the
compound from Fe (II)SO4 and and K3Fe(CN)6. The spectra of these compounds indicate that the
cation is spin-free Fe (III) and the anion is spin-paired Fe(II).

STUDY OF TIN COMPOUNDS

Sn (II) compounds have a positive isomer shift relative to gray α-tin whereas Sn (IV) compounds
exhibit a negative isomer shift. SnR4 type compunds show only singlet even when the
substituents are different, that is, the electric field at the tin nucleus is influenced only by the
nearest neighbours. However, if the character of the substituents changes strongly, quadrupole
splitting occurs. In the spectrum of pentafluoro phenyl-triphenyl-tin, a relatively large
quadrupole splitting of 1-1mms-1 is seen. Similarly a large quadrupole splitting in triphenyl-
phenyl baranyl-tin (I) (C6H5)3 Sn . C6H5 . B10H10 shows that the inductive effects due to penta
fluorophenyl and phenyl-barenyl groups are nearly equal.

Trialkyl and triaryl tin exhibit remarkable splittings. Their values in a series of organo tin halides
of the same type (RiSnHaI4-1) is proportional to the electron donor capacity of the substituents.
 NATURE OF THE CHEMICAL BOND

Sodium nitruprusside, Na2Fe(CN)5NO, was earlier formulated as Fe(II) and NO+ because it was
found to be diamagnetic. The spectrum of this compound consists of a doublet with a ΔEQ value
of 1.76 mm s-1 and a δ value of -0.165 mm s-1. The δ value is also negative for an Fe (II)
complex. Comparison of this value with other iron complexes suggests that the Fe(II) δ value is
close to that of Fe (IV).

The MB spectrum and magnetism do suggest a structure in which there is extensive π-bonding
between the odd electron in t2g set of the orbitals of iron and the odd electron on nitrogen. The
filled π-bonding orbitals has a large contribution from the nitrogen atomic orbital and the empty
π-antibonding orbital has a large contribution from the iron atomic orbital. Consequently greater
π-electron density is localised on nitrogen. The isomer shift (δ) value for iron approaches to that
of iron (IV) because of decreased shielding of the s-electron by the d-electrons. A decrease in
N--O infra red stretching frequency is observed on account of electron density being placed in
π-antibonding orbital of NO. The very large quadrupole splitting is consistent with the extensive
π-bonding in the Fe--N--O link.

Electronegativity and Isomeric Shift. There exists a direct linear relationship for the variation
of isomer shift (IS) with the difference in electronegativity (Δx) in trivalent antimony
compounds.

In case of SnX4 (X= halogen), as the electronegativity of X is increases. The ΔEQ values for the
compounds (C6H6)SnX also increase with increasing electronegativity of X because more
electronegativity X causes a larger field gradients at the nucleus. The quadrupole splitting found
in SnF4 is in agreement with the polymeric structure in which tin is hexacoordinated having
both bridiging and non bridging fluorine atoms.

Isomer Shift and Curie Point. The transition temperature below which α paramagnetic
substance gets converted into ferromagnetic because of large domains of spins aligning in
parallel orientation is know as Curie point. Below Curie temperature a single Mossbauer line
splits into six lines due to sharp decrease in electron density at the nucleus. Using 1m Ci of Co57
diffused into copper held at liquid N2 temperature as the source and iron foil of 1-66 mg/cm2
thickness and enriched in Fe57 as the absorber, Preston mapped up the Mossbauer spectrum at
different temperatures and found the Curie temperature of iron as 1046 K.

Bonding in iron Complexes.

For spin-free iron complexes in which all six ligands are equivalent, a spherical electric field at
the nucleus is expected for Fe3+(d5) and Fe2+(d6). In case of d5 , each d-orbital has one electron,
causing spherical charge distribution but there is asymmetry for the spin free d6 case. Hence,
due to field gradients at the nucleus, quadrupole splitting is detected in the spectrum of Fe(II)
complexes but not for spin-free Fe(III) complexes [Fig. 10 (a) and (b) respectively].