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Because the 4s2 electrons are lost before the 3d, the highest occupied molecular
orbitals (HOMOs) in transition metal complexes will contain the 3d electrons.
M2+ 3d1 3d2 3d3 3d4 3d5 3d6 3d7 3d8 3d9 3d10
Sc Ti V Cr Mn Fe Co Ni Cu Zn
The distribution of the 3d electrons between the d-orbitals in any given complex will
determine the magnetic properties of the complex (the number of unpaired electrons,
the total spin (S) and the magnetic moment of the complex).
Electronic transitions between the highest occupied d-orbitals will be responsible for the
energies (max) and intensities (e) of the d-d bands in the electronic spectra of metal
complexes.
Electronic transitions to and from the highest occupied d-orbitals will be responsible for
the energies and intensities of the ligand-to-metal (LMCT) and metal-to-ligand (MLCT)
charge transfer bands appearing in the electronic spectra of metal complexes.
Oh Td
High-Spin and Low-Spin Complexes for 3d4 3d7 ions
Octahedral 3d Complexes
o P(pairing energy)
Both low-spin (o P) and high-spin (P o )
complexes are found.
Tetrahedral Complexes
Td = 4/9 o hence P >> Td and tetrahedral
complexes are always high spin
Electronic structure of high-spin and low-spin Oh complexes
Other factors influencing the magnitude of -splitting
Oxidation State
o (M3+) > o(M2+)
e.g. o for Fe(III) > Fe(II).
5d > 4d >3d
e.g. Os(II) > Ru(II) > Fe(II)
I- < Br- < Cl- < SCN- < NO3- < OH- < C2O42- < H2O ~ RS- < NCS- < NH3
~ imidazole < en < bipy < phen < NO2- < PPh3 < CN- < CO
Paramagnetism arises from the spin and orbital motions of unpaired electrons
Diamagnetism arises from filled-shell electrons.
Origin of Paramagnetism
Spin angular momentum of unpaired electrons obs = M
corr
x T(K)
Orbital angular momentum of unpaired electrons
Spin-orbit coupling
For many transition metal complexes, the measured magnetic moment, obs, is very
close to the spin-only magnetic moment (orbital motion quenched).
d4 d5 d6 d7
High
Spin
P >
Low
Spin
> P
1 1.73 3.00
2 2.83 4.47
3 3.87 5.20
4 4.90 5.48
5 5.92 5.92
Orbital contributions to magnetic moments.
Quenching of orbital motion
The ligand field restricts orbital
motions of metal ion electrons.
d XZ
d YZ
[V(H2O)6]Cl3 = 3.10
[Co(NH3)6]Br2 = 4.55
K4[Fe(CN)6] =0
Antiferromagnetic Coupling of Electron Spin
M M
L
M L M
Relative energies of d-orbitals in tetragonal and square planar geometries