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Tanabe-Sugano Diagram
Jahn-Teller Effect
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Hunds Rules
numbers for total S, the total spin angular momentum and for
L, the total orbital angular momentum. It can be shown that
for full orbitals and sub-orbitals both the residual electrostatic
term (repulsion between electrons) and the spin-orbit
interaction can only shift all the energy levels together. Thus
when determining the ordering of energy levels in general
only the outer valence electrons need to be considered.
Term
S
P
D
F
G
H
I
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Certain Tanabe-Sugano diagrams (d4, d5, d6, and d7) also have
d4
--electron configurations--
d5
d2
--electron configurations--
d3
d6
--electron configurations--
d7
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d8 electron configurations
d9
Similar to d1 metal complexes, d9 octahedral metal complexes have 2D spectral
term. The transition is from the (t2g)6(eg)3 configuration (2Eg state) to the
(t2g)5(eg)4 configuration (2T2g state). This could also be described as a positive
"hole" that moves from the eg to the t2g orbital set. The sign of Dq is opposite
that for d1, with a 2Eg ground state and a 2T2g excited state. Like the d1 case, d9
octahedral complexes do not require the Tanabe-Sugano diagram to predict
their absorption spectra.
d10
There are no d-d electron transitions in d10 metal complexes because the d
orbitals are completely filled. Thus, UV-vis absorption bands are not observed
and a Tanabe-Sugano diagram does not exist.
Although they are qualitative, Tanabe-Sugano diagrams are very useful tools for
analyzing UV-vis spectra: they are used to assign bands and calculate Dq values
for ligand field splitting.
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Note:
complexes.
1
1
2
2
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Interpretation of Spectra
d3
and
Interpretation of Spectra d5
(high spin)
d8
3
1
2
3
References
Jahn-Teller Distortion
Racah, Giulio (1942). "Theory of complex spectra II". Physical Review 62: 438462.
Tanabe, Yukito; Sugano, Satoru (1954). "On the absorption spectra of complex ions I". Journal
of the Physical Society of Japan 9 (5): 753766.
3. Tanabe, Yukito; Sugano, Satoru (1954). "On the absorption spectra of complex ions II". Journal
of the Physical Society of Japan 9 (5): 766779.
4. Tanabe, Yukito; Sugano, Satoru (1956). "On the absorption spectra of complex ions III". Journal
of the Physical Society of Japan 11 (8): 864877.
5. Atkins, Peter; Overton, Tina; Rourke, Jonathan; Weller, Mark; Armstrong, Fraser; Salvador, Paul;
Hagerman, Michael; Spiro, Thomas et al (2006). Shriver & Atkins Inorganic Chemistry (4th ed.).
New York: W.H. Freeman and Company. pp. 478483.
6. Douglas, Bodie; McDaniel, Darl; Alexander, John (1994). Concepts and Models of Inorganic
Chemistry (3rd ed.). New York: John Wiley & Sons. pp. 442458.
7. Cotton, F. Albert; Wilkinson, Geoffrey; Gaus, Paul L. (1995). Basic Inorganic Chemistry (3rd d.).
New York: John Wiley & Sons. pp. 530537.
8. Bertolucci, Daniel C. (1978). Symmetry and Spectroscopy: An Introduction to Vibrational and
Electronic Spectroscopy. New York: Dover Publications, Inc.. pp. 403409, 539.
9. Lancashire, Robert John (410 June 1999), "Interpretation of the spectra of first-row transition
metal complexes", CONFCHEM, ACS Division of Chemical Education
10. Lancashire, Robert John (25 September 2006). "Tanabe-Sugano diagrams via spreadsheets".
Retrieved 29 November 2009.
11. Jrgensen, Chr Klixbll (1954). "Studies of absorption spectra IV: Some new transition group
bands of low intensity". Acta Chem. Scand. 8 (9): 15021512.
12. Jrgensen, Chr Klixbll (1954). "Studies of absorption spectra III: Absoprtion Bands as Gaussian
Error Curves". Acta Chem. Scand. 8 (9): 14951501.
1.
2.
Long axial
Cu-O bonds
= 2.45
four short
in-plane
Cu-O bonds
= 2.00
[Cu(H2O)6]2+
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The Jahn-Teller (J-T) theorem states that in molecules/ ions that have a degenerate
ground-state, the molecule/ion will distort to remove the degeneracy. This is a
fancy way of saying that when orbitals in the same level are occupied by different
numbers of electrons, this will lead to distortion of the molecule. For us, what is
important is that if the two orbitals of the eg level have different numbers of
electrons, this will lead to J-T distortion. Cu(II) with its d9 configuration is
degenerate and has J-T distortion:
High-spin Ni(II) only one way
of filling the eg level not
degenerate, no J-T distortion
d8
energy
Ni(II)
eg
t2g
eg
eg
t2g
t2g
four short
in-plane
Cu-O bonds
= 2.00
[Cu(H2O)6]2+
J-T distortion lengthens axial Cu-Os
[Ni(H2O)6]2+
no J-T distortion
water
N
Cu
Short
in-plane
Cu-N
bonds of
2.03
ethylenediamine
CCD:AZAREY
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12
10
N
Cu
logK1(en).
Short in-plane
Cu-N bonds of
2.07
N
N
doublehumped
curve
8
6
Zn2+
Ca2+
CCD:TEDZEI
LFSE
Mn2+
d2
d3
d4
d5
d6
d7
0 .4o .8 1.2 .6 0 .4 .8
d8
10 11
d-electrons configuration
rising baseline
due to ionic
contraction
do
Extra
stabilization
due to J-T
distortion
= CFSE
d9
1.2 .6
d10
energy
0
eg
eg
t2g
d4 high-spin
Cr(II)
Mn(III)
t2g
d7 low-spin
Co(II)
Ni(III)
eg
eg
t2g
t2g
d8 low-spin
d9
Cu(II)
Ag(II)
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eHigh
spin
Low
spin
1 2 3 4 5 6 7 8 9 10
* * * s
- w w * *
w w - w w -
*
-
Many transition metal complexes exhibit strong chargetransfer absorptions in the UV or visible range. These are
much more intense than dd transitions, with extinction
coefficients 50,000 L/mol-cm (as compared to 20 L/molcm for dd transitions).
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Latihan Soal
3. Jelaskan 4 faktor yang mempengaruhi nilai 10Dq (o)!
4. Gambarkan dua orbital molekul dari kompleks [NiCl4]2(Ar Ni = 28) ketika bersifat diamagnetik maupun
paramagnetik!
10