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energy
eg
3d sub-shell
d-shell split by presence of ligand donor-atoms
t2g
Co(III) in complex
The d-orbitals:
z
y
z
y
z
y
dyz
x
z
dxy
y
x
z
dxz
y
dz2
dx2-y2
the eg set
the egset
z
y
z
y
z
y
dyz
dz2
dx2-y2
the three orbitals of the t2g set lie between the ligand donor-atoms (only dyz shown)
the two orbitals of the eg set lie along the Cartesian coordinates, and so are adjacent to the donor atoms of the ligands, which raises the eg set in energy
eg
3d sub-shell
d-shell split by presence of ligand donor-atoms
t2g
Co(III) in octahedral complex
energy
eg
= 26,600 cm-1
eg
= 15,000 cm-1
t2g
t2g
[Cr(CN)6]3[CrF6]3-
eg
energy
>P
eg
<P
t2g
low-spin d6
electrons fill the t2g level first. In this case the complex is diamagnetic
t2g
high-spin d6
electrons fill the whole d subshell according to Hunds rule
eg
energy
>P
eg
<P
t2g
low-spin d5 ([Fe(CN)6]3-)
electrons fill the t2g level first. In this case the complex is paramagnetic
t2g
high-spin d5 ([Fe(H2O)6]3+)
electrons fill the whole d sub-shell according to Hunds rule
eg
energy
>P
eg
<P
t2g
low-spin d7 ([Ni(bipy)3]3+)
The d-electrons fill the t2g level first, and only then does an electron occupy the eg level.
t2g
high-spin d7 ([Co(H2O)6]3+)
electrons fill the whole d sub-shell according to Hunds rule
eg
energy
eg
<P
>> P
t2g
low-spin d6 ([Co(CN)6]4-)
electrons fill the t2g level first. In this case the complex is diamagnetic
t2g
high-spin d5 ([CoF6]3-)
electrons fill the whole d sub-shell according to Hunds rule
I- < Br- < Cl- < F- < OH- H2O < NH3 < CN-
O S
S-donors between Br and Cl
F Cl
?
very little data on P-donors may be higher than N-donors
Br
I
O
-
O
-
H 3C O O-
CH3 H 2N NH2 en
O O oxalate
acetylacetonate
H 2N dien
N H
NH2
N bipyridyl
1,10-phen
CFSE = (0.4n(t2g)
the t2g and eg levels respectively.
0.6n(eg))
[Cr(en)3]3+
eg
t2g
= 22,900 cm-1 = 21,900 cm-1
CFSE = 22,900(0.4 x 6 0.6 x 0) = 54,960 cm-1
eg
t2g
CFSE = 21,900(0.4 x 3 0.6 x 0) = 26,280 cm-1
[Zn(en)3]3+
eg
t2g
= 22,900 cm-1 = not known
CFSE = 10,000(0.4 x 3 0.6 x 2) = 0 cm-1
eg
t2g
CFSE = (0.4 x 6 0.6 x 4) = 0 cm-1
This pattern of variation CFSE leads to greater stabilization in the complexes of metal ions with high CFSE, such as Ni(II), and lower stabilization for the complexes of M(II) ions with no CFSE, e.g. Ca(II), Mn(II), and Zn(II). The variation in CFSE can be compared with the log K1 values for EDTA complexes on the next slide:
Ni2+
doublehumped curve
Ca2+
1 2 3 4 5
Mn2+
6 7 8
Zn2+
9 10 11
no of d-electrons
logK1(EDTA) .
18 16 14
12 10 0
Ca2+
1 2 3 4 5 6
10 11
no of d-electrons
= CFSE
logK1(en) .
8 6 4 2 0 0 1 2 3 4
10 11
no of d-electrons
20
logK1(tpen).
15 10 5 0 0
no of d-electrons
Mn(II) < Fe(II) < Co(II) < Ni(II) < Cu(II) > Zn(II)
We see that this order holds for the ligand EDTA, en, and TPEN on the previous slides. One notes that Cu(II) does not follow the order predicted by CFSE, which would have Ni(II) > Cu(II). This will be discussed under Jahn-Teller distortion of Cu(II) complexes, which leads to additional stabilization for Cu(II) complexes over what would be expected from the variation in CFSE.