• d8 system
• Ni(II) has A2g ground state in an octahedral field. Spin-orbit coupling leads to greater g value
than that for a free electron and splits A2g configuration. This is because of the zero field
splitting and it is very anisotropic. Therefore EPR spectra of Ni(II) octahedral complexes are
difficult to detect.
• The Ni(II) square planar complexes are diamagnetic in nature. Therefore EPR spectra are not
recorded for them. They are used to dilute the spins of copper (II) complexes.
• d9 system
• The ground state of an octahedral d9 system is Eg. Since there is large Jahn-Teller distortion,
the spectrum is recorded at room temperature.
• In tetragonal complexes the ground state is 2A which will give sharp EPR lines. The square
planar complex has the same symmetry as tetragonally distorted octahedron. So there are two
resonances with g11 and g1.
• For example, Cu(II) tetraphenyl phorphine complex consists of four groups of parallel
resonances, three are seen at low field.
(i) EPR spectrum of Bis salicylaldiminecopper(II) complex
• Bis salicylaldiminecopper(II) complex : CuL2 ; L = Salicylaldimine = C6H4 CHO = NH
{Bi dentate ligand with O & N as donors) [I : Cu = 3/2 ; N = 1 ; H = ½ ]
• The spectrum was obtained on a solid and is not isotropic. Four main group of lines result
from coupling of the 63Cu nucleus (I = 3/2) with the electron. But, due to overlapping, we get
44 lines as 4 set each consisting of 11 lines. The intensity of lines in each set is in the ratio
1 : 2 : 3 : 4 : 5 : 6 : 5 : 4 : 3 : 2 : 1.
(ii) EPR spectrum of [Cu(bpy)3]2+
• When one electron couples with 63Cu (For Cu, I = 3/2) four lines of N N
equal intensity are obtained. 2nI+1 = 2(1)(3/2) +1 = 3 + 1 = 4. N
C u
N
• Each bipyridyl ligand contains 2 N atoms. The electron on Cu also
N N
couples with these 6 N atoms to give 13 lines each. (for N, I = 1),
2nI+1 = 2 (6) (1) +1 = 13.
• Total lines = 4 x 13 = 52 lines are obtained.
(iii) EPR spectrum of [Cu(Phen)Cl2],
• When one electron couples with 63Cu (I, Cu = 3/2) four lines of equal
intensity are obtained, 2nI+1 = 2(1)(3/2) +1 = 3 + 1 = 4.
• 1,10-phenanthroline ligand contains 2 N atoms. The electron on Cu N N
also couples with these 2 N atoms to give 13 lines each, 2nI+1 = 2 (2) C
u
C
l
(1) +1 = 5. C
l
• Total = 4 x 5 = 20 lines are obtained.
• If 35Cl, I = 3/2, also interact, this will further split the spectrum into 7
lines (2nI+1 = 2(2)(3/2)+1 = 7).
• Total 4 x 5 x 7 = 120 lines are expected.
(iv) EPR spectrum of [(NH3)5Co-O2-Co(NH3)5]5+
• The EPR spectrum of [(NH3)5Co-O2-Co(NH3)5]5+ consists of 15 lines. There are four
possibilities.
• Two Co(III) is connected by O2 bridge. In this case a single line is expected.
• Co(III) and Co(IV) are connected by means of peroxo bridge O2. In this case 8 lines are
expected. I = 7/2 for Co.
• Two equivalent Co atoms owing to equal interaction of one unpaired electron with both
cobalt atoms. Therefore 15 lines are expected (2 x 2 x 7/2 + 1).
• Interactions of electrons with both Co atoms but more with one than with other. In this case
64 lines are expected.
• Among the four possibilities, (i) and (ii) are most probable. An 17O hyperfine result
would be required to determine the importance of structure (i).
(v) EPR spectrum of Co3(CO)9Se
• The EPR spectrum of this complex is given below. The 22-line spectrum indicates
that the one unpaired electron in this system is completely delocalized over the three
cobalt atoms. (I Co = 7/2). 2x3(7/2)+1=22.
• The intensity ratio is [Link].
This in effect gives rise to an oxidation state of +2/3 for each cobalt atom. For Se, I =
0, hence it does not give hyperfine splitting.
(A) Basic molecular geometry of the Co3(CO)9Se complex.
(B) The EPR spectrum of a single crystal of FeCo2(CO)Se doped with about 0.5% of
paramagnetic Co3(CO)Se.
(vi) EPR spectrum of Co3(CO)9Rh
• Three ESR transitions are expected, but the electrons also couple with 3 Co atoms.
• For Co, I = 7/2, 2nI+1 = 2(3)(7/2)+1= 22).
• Rh (I=1/2) also couple and hence each line will be further
split into a doublet, total 44 lines would be obtained.
(vii) EPR spectrum of [CoF6]4-
• [CoF6]4-, the unpaired electrons can also couple with 6 F ligands which are directly
attached to give super hyperfine splitting, 2nI+1 = 2 x 6 (1/2) + 1= 7.
• Hence 3 x 8 x 7 = 168 lines are expected.
• Theoretically, [CoF6]3- is expected to give 168 lines spectrum.
(viii) EPR spectrum of [CrF6]3-
• An unpaired electron on a Cr3+ couples to the Cr nucleus giving rise to an 8-line
splitting pattern, 2I+1 = 2(7/2)+1= 8.
• The unpaired electrons can also couple with 6 F ligands which are directly
attached to give super hyperfine splitting, 2nI+1 = 2x6(1/2)+1= 7.
• So in [CrF6]3-, 3 x 8 x 7 = 168 lines are expected.
(ix) EPR spectrum of [VO(H2O)6]2+
• V(IV) has a 3d1 electron configuration and hence one unpaired electron. For
vanadium, I = 7/2 (almost 100% abundant).
• The unpaired electron couples only to 51V (16O has I = 0), expected to give eight
line pattern. But two overlapping eight-line patterns are obtained.
• This arises from the fact that one of the axes in the complex is different to the
other two, resulting in the tetragonal spectrum, with a parallel and perpendicular
component.
• For VO2+, g‖ = 2.0023 - 8k𝜆/ΔEx2-y2; g= 2.0023 - 2kʹ𝜆/ΔExz, yz
• Since 𝜆 is positive, both gs are less than the free electron value: typical ranges are
1.97 > g‖ > 1.93 and 2.0 > g1> 1.96.
• Many measurements are made on solution, when only the average g-value is
obtained; this is usually reported as giso.
(x) EPR spectrum of [Fe(CN)5NO]3−
• The ESR spectrum of a solution of [Fe(CN)5NO]3-
consists of three equally-spaced hyperfine lines, while
that of [Mn(CN)5NO]2- has six hyperfine lines.
• Shows unpaired electron interacting with N (14N, I=1) of NO ligand. (Fe is 98% I=0, and
~2% 57Fe, I=1/2)
• The spectrum of [Mn(CN)5NO]2- has six lines, showing electron interacting with 55Mn
nucleus (100%, I=5/2), but not with NO ligand.
• Consider NO as neutral (with one "extra" electron) or as NO+ (isoelectronic with CN-)
• So [Fe(CN)5NO]3- is either an Fe(II) (d6) complex with NO or an Fe(I) (d7) complex with
NO+.
• Either way, there are 7 valence electrons. Six will occupy the t2g orbitals and the seventh will
be in an eg orbital directed towards the ligands (i.e. towards the N in NO).
• [Mn(CN)5NO]2- is either a Mn(III) (d4) complex with NO, or a Mn(II) (d5) complex with
NO+.
• Either way, there are 5 valence electrons. These will occupy the t2g orbitals, and the unpaired
electron will therefore be associated with the metal center.
