You are on page 1of 9

Five Slides About: UV-Vis Spectroscopy and Tanabe-Sugano Diagrams

Sabrina G. Sobel Hofstra University Sabrina.G.Sobel@hofstra .edu

Created by Sabrina.G.Sobel, Hofstra University ( Sabrina.G.Sobel@hofstra.edu) and posted on VIPEr (www.ionicviper.org)

on March 8, 2014. Copyright Sabrina G. Sobel 2014. This work is licensed under the Creative Commons Attribution-NonCommerical-ShareAlike 3.0 Unported License. To view a copy of this license visit

d-Orbital Splitting in Transition Metal Complexes

e g

e g
e g

t 2g

2g
2g
2g

t 2

t 2
t 2
t 2

e

e
e

Octahedral (O h ) symmetry:

d-orbitals split into t 2g and e g

o

sets

o is the splitting energy, and is

dictated by ligand field strength (see spectrochemical series)

Tetrahedral (T d ) symmetry:

d-orbitals split into e and t 2 sets

T is always smaller than o

since total ligand field strength is less

CN - , CO > NO 2 - , phen > bpy > SO

3

Spectrochemical Series

3

2-

> NH

> NCS - > H 2 O > OH - > F -

> Cl - > SCN - > Br - > I -

UV-Vis Spectroscopy of Transition Metal Complexes

Symmetry Rules:

LaPorte: allowed transitions occur between orbitals of opposite symmetry WRT inversion (gerade (even) and ungerade (odd) in character tables)

Spin Multiplicity: allowed transition occur when spin multiplicity is unchanged

d 0 metal cations: charge-transfer transitions

LaPorte allowed; ligand * to metal d orbital

d 1 to d 9 metal cations: dd transitions

LaPorte forbidden; same orbital type

d 10 metal cations: no dd transitions because the orbitals are filled

d d Transitions and Color

TM complex (d 1 to d 9 ) absorbs visible light

Transmitted light is opposite color to absorbed light Energy of absorbed light is proportional to Strong field ligand: low nm Weak field ligand: high nm Example: Fe(phen) 3 2+

max = 508 nm (green) Transmitted color: red- orange

d  d Transitions and Color • TM complex (d 1 to d 9 ) absorbs

d d Transitions and Color

d  d Transitions and Color Cobalt complexes with: (a) CN , (b) NO , (c)

Cobalt complexes with: (a) CN , (b) NO 2 , (c) phen, (d) EN, (e) NH 3 , (f) gly, (g) H 2 O, (h) oxalate 2 , (i) CO 3

2–

.

Complexes are arranged in order of decreasing oct Color transmitted increases in energy from yellow olive

Russell-Saunders Coupling

Review:

Example: Cr(II); d 4

  • 1. Orbital diagram

Determining ground state of Transition Metal cations

  • 1. Draw d-orbitals and fill with # electrons for desired ion

  • 2. Calculate Spin Multiplicity = #unpaired electrons +1 = S

  • 3. Find maximum M L (m l = -2,

-1, 0, 1, 2 for d orbitals) =

L

  • 4. Ground state term:

S L = (step

L : -2 -1 0 +1 +2
L :
-2
-1
0
+1
+2
  • 2. 4+1 = 5

  • 3. 2+1+0+(-1) = 2 D

  • 4. 5 D is the ground state term

Spin-allowed transitions will be pentet to pentet

O h Tanabe-Sugano Diagrams

Symmetry lowering from spherical to octahedral electrical field is applied to ground state and excited state terms

Relative energies of states are plotted against ligand field strength

O Tanabe-Sugano Diagrams • Symmetry lowering from spherical to octahedral electrical field is applied to ground

Degenera

States in an octahedral field

d 4 ion

States in an octahedral field d ion g.s.

g.s.

Term

 

cy

S

1

A 1g

P

3

T 1g

D

5

F

7

A 2g

G

9

H

11

E g + T 2g

+ T 1g

+ T 2g

A 1g + E g + T 1g + T 2g

E g + T 1g + T 1g + T 2g

O h T-S Diagram for a d 4

O h Tanabe-Sugano Diagrams

• • • • B = Racah Parameter; takes into account electron repulsion energy X-axis: /B
B = Racah Parameter;
takes into account
electron repulsion
energy
X-axis: /B
Y-axis: E/B
High spin vs. low spin
e g
t 2g
5 D
3 G

Spin allowed transitions:

5 E to 5 T 2 (UV-Vis range)

3 T 1 to 3 E (large energy gap!)

O h T-S Diagram for a d 4 ion
O h T-S Diagram for a d 4
ion

[Cr(CH 3 CO 2 ) 2 (H 2 O)] 2 is brick red; CrCl 2 (H 2 O) 4 is green