UV-visible spectroscopy

Usama El-Ayaan

the Period 4 transition metals

Usama El-Ayaan

Colors of representative compounds of the Period 4 transition metals

sodium chromate titanium oxide nickel(II) nitrate hexahydrate potassium ferricyanide

zinc sulfate heptahydrate

scandium oxide vanadyl sulfate dihydrate

manganese(II) chloride tetrahydrate

cobalt(II) chloride hexahydrate

copper(II) sulfate pentahydrate

Usama El-Ayaan

Aqueous oxoanions of transition elements

One of the most characteristic chemical properties of these elements is the occurrence of

multiple oxidation states.

Mn(II) Mn(VI) Mn(VII)

Mn(VII) Cr(VI) V(V)

Usama El-Ayaan

Effects of the metal oxidation state and of ligand identity on color

[V(H2O)6]2+

[V(H2O)6]3+

[Cr(NH3)6]3+

[Cr(NH3)5Cl ]2+

Usama El-Ayaan

Linkage isomers

Usama El-Ayaan

Complementary colour

Usama El-Ayaan

Usama El-Ayaan

The five d-orbitals in an octahedral field of ligands

Usama El-Ayaan

Splitting of d-orbital energies by an octahedral field of ligands

is the splitting energy

Usama El-Ayaan

The effect of ligand on splitting energy

Usama El-Ayaan

Electronic Spectroscopy of Transition Metal Complexes

Chemistry 412 Experiment 1

Usama El-Ayaan

What is electronic spectroscopy? Absorption of radiation leading to electronic transitions within a molecule or complex

Absorption 104

[Ru(bpy)3]2+

Absorption 10

[Ni(H2O)6]2+

200 UV

400 visible

700

~14 000

25 000 visible / cm-1 (frequency)

50 000 UV

/ nm (wavelength)

UV visible

= =

higher energy transitions - between ligand orbitals lower energy transitions - between d-orbitals of transition metals - between metal and ligand orbitals
Usama El-Ayaan

Absorption maxima in a visible spectrum have three important characteristics

1.

number (how many there are)

This depends on the electron configuration of the metal centre 2. position (what wavelength/energy)

This depends on the ligand field splitting parameter, oct or tet and on the degree of inter-electron repulsion 3. intensity

This depends on the "allowedness" of the transitions which is described by two selection rules

Usama El-Ayaan

Selection Rules
In electronic spectroscopy there are three selection rules which determine whether or not transitions are formally allowed: 1. Spin selection rule: S = 0 allowed transitions: singlet singlet or triplet triplet forbidden transitions: singlet triplet or triplet singlet Changes in spin multiplicity are forbidden

Singlet state: All electrons in the molecule are spin-paired Triplet state: One set Usama El-Ayaanspins is unpaired of electron

Selection rules
2.

Transition metal complexes get around this rule through M-L vibrations, which temporarily removes the center of symmetry

Laporte selection rule: there must be a change in the parity (symmetry) of the complex Laporte-allowed transitions: g u Laporte-forbidden transitions: g g or

uu

g stands for gerade compound with a center of symmetry u stands for ungerade compound without a center of symmetry
3. Selection rule of = 1 ( is the azimuthal or orbital quantum number, where = 0 (s orbital), 1 (p orbital), 2 (d orbital), etc.) allowed transitions: s p, p d, d f, etc. forbidden transitions: s s, d d, p f, etc.
Usama El-Ayaan

Energy of transitions

Excited State molecular rotations lower energy (0.01 - 1 kJ mol-1) microwave radiation

electron transitions higher energy (100 - 104 kJ mol-1) visible and UV radiation

Ground State

molecular vibrations medium energy (1 - 120 kJ mol-1) IR radiation During an electronic transition the complex absorbs energy electrons change orbital
Usama El-Ayaan the complex changes energy state

Absorption of light [Ti(OH2)6]3+ = d1 ion, octahedral complex

white light 400-800 nm blue: 400-490 nm
Ti

3+

yellow-green: 490-580 nm red: 580-700 nm

This complex has a light purple colour in solution because it absorbs green light
/ nm

Usama El-Ayaan

max = 510 nm

The energy of the absorption by [Ti(OH2)6]3+ is the ligand-field splitting, o

ES ES

eg
h
GS

eg o t2g
GS

t2g

complex in electronic Ground State (GS) [Ti(OH2)6]3+

d-d transition

complex in electronic excited state (ES) o is 243 kJ mol-1 20 300 cm-1

max = 510 nm

Usama El-Ayaan An electron changes orbital; the ion changes energy state

d2 ion

Electron-electron repulsion

z2 x2-y2

eg

z2 x2-y2

eg

t2g xy xz yz xy xz yz

t2g

xz + z2 z y x

xy + z2 z y x

lobes overlap, large electron repulsion

lobes far apart, small electron repulsion

Usama do not These two electron configurations El-Ayaan have the same energy

Deriving term symbols in a free ion

Electron configurations of the same energy are collected together into terms

- an electron is completely defined by 4 quantum numbers n = 1,2,3 (energy and distance from the nucleus ie. what shell) l = 0, 1, 2orbital angular momentum (what sort {shape} of orbital, s, p, d) ml = -l+l component of l (what kind of orbital, eg. for d: xy, xz) ms = spin angular momentum (contribution from unpaired electrons, spin 1/2)

- an ion can be defined using ionic quantum numbers made up of contributions from all the electrons in the ion.. ..theseEl-Ayaan the whole ion Usama define

Russel Saunders Coupling Ionic quantum numbers: L = 0, 1, 2total orbital angular momentum (term) ML = -L+L component of L (ML = ml) S = total spin quantum number (S = s) Ms = -S.+S component of S (MS = ms) Each electronic state has its own term symbol spin multiplicity 2S+1 L=0 L=1 L=2 L=3 S term P term D term F term

L
Usama El-Ayaan

Within each term, there can be several degenerate microstates with different ML and MS

Microstates e.g. for a free d2 ion

10 ways of arranging 2 electrons in 5 degenerate d-orbitals (Hund's rules apply)

etc

low repulsion (7 microstates) xy + z2 xy + xz xy + yz xz + yz x2-y2 + z2 x2-y2 + yz x2-y2 + xz

high repulsion (3 microstates) xz + z2 yz + z2 xy + x2-y2 ML = -1, 0, 1

ML = -3, -2, -1, 0, 1, 2, 3

spin multiplicity

2S+1

L
Usama El-Ayaan

orbital angular momentum

ML = ml For d-orbitals ml = -2 -1 0 z2 1 2

x2-y2 yz

xz xy

low repulsion (7 microstates) xy + z2 xy + xz xy + yz xz + yz x2-y2 + z2 x2-y2 + yz x2-y2 + xz

high repulsion (3 microstates) xz + z2 yz + z2 xy + x2-y2 ML = -1, 0, 1

ML = -3, -2, -1, 0, 1, 2, 3

For ML = -3.3 For ML = -1.1

L=3 L=1

F term P term

Usama El-Ayaan

2S+1

F and P

Total spin S

no. of electrons x spin on an electron 2 x 1/2 (2S + 1) = 3

S=1

Spin multiplicity =

For a free d2 ion with two parallel spins there are two terms

low energy

high energy

Usama El-Ayaan

Which is the Ground State?

3P

E
3F

States of the same spin multiplicity

E = 15 B

B is the Racah parameter and is a measure of inter-electron repulsion within the whole ion

Relative strength of coupling interactions: MS = ms

>

MUsama El-Ayaan L = ml

>

ML - MS

Deriving the Ground State Term (Hund's rules) 1. States with the highest spin multiplicity (2S+1) will be lowest in energy (S = no. of e- x spin 1/2) e.g. for a d5 ion 6S < 4G

2. Of two states with the same S, the one with higher L is of lower energy L = 0, S term; L = 1, P term; L = 2, D term; L = 3, F term

e.g. for a d2 ion 3F < 3P

These rules are only applicable to the ground state

Usama El-Ayaan

What are the ground state terms for the configurations p2 and d2?

p2:

1D

3P

1S

The ground state must be 3P because this has the largest spin multiplicity

d2:

1G

3F

1D

3P

1S

The ground state is either 3F or 3P because these have the largest spin multiplicity Of the two, 3F must be the ground state because it has the largest value of L (when L = 2, P term; when L = 3, F term)

Usama El-Ayaan

Ground States in free ions d3 -2 -1 0 1 2

ML = -33 MS = 3/2

L=3 2S+1 =

F term 4

4F

d4

-2

-1

ML = -22 MS = 4/2

L=2 2S+1 =

D term 5

5D

d5

-2

-1

ML = 0 MS = 5/2

L=0 2S+1 =

S term 6

6S

d6

-2

-1

ML = -2.2 MUsama El-Ayaan S = 2

L=2 2S+1 =

D term 5

5D

Ground States in free ions

d7

-2

-1

ML = -3.3 MS = 3/2

L=3 2S+1 =

F term 4

4F

d8

-2

-1

ML = -3.3 MS = 2/2

L=3 2S+1 =

F term 3

3F

d9

-2

-1

ML = -22 MS = 1/2
Usama El-Ayaan

L=2 2S+1 =

D term 2

2D

Ground State Terms for all electron configurations

Ground State d1 d2 d3 d4 d5 d9 d8 d7 d6
2D 3F 4F 5D 6S 3P 4P

d-d transitions in high spin complexes

Usama El-Ayaan

Effect of a crystal field on the free ion term of a d1 complex d1 d6

tetrahedral field

free ion

octahedral field
2E g

2T

6 Dq
2D

4 Dq
2E 2T 2g

Usama El-Ayaan

Energy level diagram for d1 ions in an Oh field

Energy

2E g

2D

2T

2g

ligand field strength, oct

For d6 ions in an Oh field, the splitting is the same, but the multiplicity of the states is 5,

ie 5Eg and 5T2g

Usama El-Ayaan

d1 oct
2E g 2T 2g 2D

2E g

[Ti(OH2)6]3+

2T

2g

10 000

20 000

30 000

/ cm-1
Orgel diagram for d1, d4, d6, d9 E T2g or T2 D Eg or E

T2g or T2

Eg or E d1, d6 tetrahedral d4, d9 octahedral d1, d6 octahedral d4, d9 tetrahedral Usama El-Ayaan LF strength 0

The Jahn-Teller Distortion: Any non-linear molecule in a degenerate electronic state will undergo distortion to lower it's symmetry and lift the degeneracy Degenerate electronic ground state: Non-degenerate ground state: T or E A d3 d5 (high spin) d6 (low spin) d8
4A 2g 6A 1g 1A 1g 3A 2g

2E g

2B 1g 2A 1g

[Ti(H2O)6]3+, d1

2T

2g

10 Usama El-Ayaan 000

20 000

30 000

/ cm-1

Racah Parameters Free ion [Co2+]: B = 971 cm-1

[Co(H2O)6]2+ [CoCl4]2-

d7 octahedral complex 15 B' = 13 800 cm-1 B' = 920 cm-1

d7 tetrahedral complex 15 B' = 10 900 cm-1 B' = 727 cm-1

B' = 0.95 B Nephelauxetic ratio,

B' = 0.75 B

is a measure of the decrease in electron-electron repulsion on complexation

Usama El-Ayaan

The Nephelauxetic Effect

cloud expanding

- some covalency in M-L bonds M and L share electrons -effective size of metal orbitals increases -electron-electron repulsion decreases

Nephelauxetic series of ligands F- < H2O < NH3 < en < [oxalate]2- < [NCS]- < Cl- < Br- < INephelauxetic series of metal ions Mn(II) < Ni(II) Co(II) < Mo(II) > Re (IV) < Fe(III) < Ir(III) < Co(III) < Mn(IV)
Usama El-Ayaan

Selection Rules Transition

Spin forbidden Laporte forbidden Spin allowed Laporte forbidden

10-3 1

complexes
Many d5 Oh cxs [Mn(OH2)6]2+

1 10

Many Oh cxs [Ni(OH2)6]2+ Some square planar cxs [PdCl4]26-coordinate complexes of low symmetry, many square planar cxs particularly with organic ligands Some MLCT bands in cxs with unsaturated ligands Acentric complexes with ligands such as acac, or with P donor atoms Many CT bands, transitions in organic species
Usama El-Ayaan

10 100

100 1000

Spin allowed Laporte allowed

102 103 102 104

103 106

The Spectrochemical Series

eg

eg

t 2g

I- < Br- < S2- < SCN- < Cl-< NO3- < F- < OH- < ox2< H2O < NCS- <

CH3CN < NH3 < en < bpy

< phen < NO2- < phosph < CN- < CO

t 2g

weak field ligands e.g. H2O high spin complexes

strong field ligands e.g. CNlow spin complexes

The Spin Transition

Usama El-Ayaan

d5
4T 2g

Tanabe-Sugano diagrams
2A 1g 4T 1g 4E g 4T 2g 4A 4 1g, E 2A 1g 2T 1g 2T 2g 2E g 4A 2 2g, T1g 4T 2g 6A 1g 4T 1g

E/B

All terms included Ground state assigned to E = 0 Higher levels drawn relative to GS Energy in terms of B High-spin and low-spin configurations Critical value of

2T 2g

WEAK FIELD

/B

STRONG FIELD

Usama El-Ayaan

Tanabe-Sugano diagram for d2 ions [V(H2O)6]3+: Three spin allowed transitions E/B

10

30 000

20 000

10 000 / cm-1

1 = 17 800 cm-1 2 = 25 700 cm-1

visible visible

3 = obscured by CT transition in UV

25 700 = 17 800

1.44

/B

32

3 = 2.11 = 2.1 x 17 800 /B = 32

Usama El-Ayaan

3 = 37 000 cm-1

E/B 1 = 17 800 cm-1 2 = 25 700 cm-1 2 1

E/B = 43 cm-1 E/B = 30 cm-1

E/B = 43 cm-1 B o / B o = = =

E = 25 700 cm-1

600 cm-1 32 19 200 cm-1

Usama El-Ayaan

/B = 32

Tanabe-Sugano diagram for d3 ions [Cr(H2O)6]3+: Three spin allowed transitions E/B

1 = 17 400 cm-1 2 = 24 500 cm-1

visible visible

3 = obscured by CT transition 24 500 = 17 400 /B = 24 1.41

3 = 2.11 = 2.1 x 17 400 3 = 36 500 cm-1

/B = 24

Usama El-Ayaan

Calculating 3

1 = 17 400 cm-1 2 = 24 500 cm-1

E/B

When

1 = E =17 400 cm-1 E/B = 24 B = 725 cm-1 2 = E =24 500 cm-1 E/B = 34 B = 725 cm-1

so When

E/B = 34

cm-1

so

E/B = 24 cm-1

If /B = 24 = 24 x 725 = 17 400 cm-1

/B = 24

Usama El-Ayaan

d0 and d10 ions Zn2+ d10 ion white d0 ion d0 ion d0 ion d0 ion

d0 and d10 ion have no d-d transitions

TiF4 TiCl4 TiBr4 TiI4

white white orange dark brown

[MnO4][Cr2O7]-

Mn(VII) Cr(VI)

d0 ion extremely purple d0 ion bright orange

[Cu(MeCN)4]+ [Cu(phen)2]+

Cu(I) Cu(I)

d10 ion colourless d10 ion dark orange

Charge Transfer Transitions Usama El-Ayaan

Metal-to-ligand charge transfer MLCT transitions

Ligand-to-metal charge transfer LMCT transitions

Charge Transfer Transitions

d-d transitions eg* t2g* Md

L
Usama El-Ayaan

Transition Metals, Compounds and Complexes or Electronic Spectroscopy of Transition Metal Complexes
Dr. E.R. Schofield

Lecture 3:

Interpretation of weak field spectra Electronic spectra from Orgel diagrams Orgel diagram for d2, d3, d7, d8 ions

Usama El-Ayaan

d1 d6

d4 d9

Orgel diagram for d1, d4, d6, d9 Energy T2g or T2 D Eg

or

T2g or T2 Eg or E d1, d6 tetrahedral d4, d9 octahedral 0 d1, d6 octahedral d4, d9 tetrahedral

ligand field strength

Usama El-Ayaan

d1 oct
2E g 2T 2g 2D

2E g

[Ti(OH2)6]3+

2T

2g

10 000

20 000

30 000

/ cm-1
Orgel diagram for d1, d4, d6, d9 E T2g or T2 D Eg or E

T2g or T2

Eg or E d1, d6 tetrahedral d4, d9 octahedral d1, d6 octahedral d4, d9 tetrahedral Usama El-Ayaan LF strength 0

Effect of a ligand field on Ground State Terms GS d1 d2 d3 d4 d5 d9 d8 d7 d6

2D 3F 4F 5D 6S 3P 4P

free ion

ligand field

T2(g) and E(g)

GS d1 d2 d3 d4 d5 d9 d8 d7 d6
2D 3F 4F 5D 6S 3P 4P

free ion

ligand field

?
F
Usama El-Ayaan

Octahedral d2 complex

d2 d7

3P:

high repulsion

In a LF, these orbitals are unaffected

xz + z2 yz + z2 xy + x2-y2

3T

1g

3F:

low repulsion

In a LF, orbitals in the t2g set go down in energy, orbitals in the eg set go up in energy eg eg singly degenerate, high energy

x2-y2 + z2 x2-y2 + yz x2-y2 + xz xy + z2 xy + xz xy + yz xz + yz

3A 2g

3T

2g

eg t2g

triply degenerate, medium energy

3T

1g

t2g t2g

triply degenerate, low energy

Usama El-Ayaan

Octahedral d3 complex (same terms, different spin)

4P:

d3 d8

high repulsion
4T 1g

In a LF, these orbitals are unaffected

4F:

low repulsion

The order of energy levels is the opposite to that for a d2 ion

4T 4T 1g

2g

4A 2g

Usama El-Ayaan

Orgel diagram for d2, d3, d7, d8 ions Quantum Mixing

Energy

A2 or A2g T1 or T1g P T1 or T1g T1 or T1g T2 or T2g

T2 or T2g T1 or T1g A2 or A2g d2, d7 tetrahedral 0 d2, d7 octahedral

d3, d8 octahedral d3, 8 Usama El-Ayaan d tetrahedral Ligand field strength (Dq)

Energy level diagram for oct d2, d7, tet d3, d8 T1(g) x P A2(g) 15 B 10 Dq T2(g) F 2 Dq 6 Dq 15 B' 15 B > 15 B'

T1(g)
Usama El-Ayaan

Calculating B' and x 3

A x

d7 octahedral complex
[Co(H2O)6]2+

4T 1g

3 2 1

4A 2g

2
15 B' 10 Dq
v / cm-1

4T 2g

1
2 Dq 6 Dq

25 000

20 000

15 000

10 000

1 = 8 000 cm-1 2 = 16 000 cm-1 3 = 19 400 cm-1

x
4T 1g

Usama El-Ayaan

Orgel diagram for d2, d3, d7, d8 ions

Energy

A2 or A2g T1 or T1g P T1 or T1g T1 or T1g T2 or T2g

T2 or T2g T1 or T1g A2 or A2g d2, d7 tetrahedral 0 d2, d7 octahedral

d3, d8 octahedral d3, 8 Usama El-Ayaan d tetrahedral Ligand field strength (Dq)

Energy level diagram for oct d2, d7, tet d3, d8 A2(g) 3 T1(g) 2 P x 10 Dq

1: 2: 3:

x + 8 Dq 2 x + 6 Dq + 15 B' x + 18 Dq

1: 2: 3:

T2(g) T1(g)(P) A2(g)

T1(g) T1(g) T1(g)

15 B F

T2(g) 1 2 Dq 6 Dq

15 B'

T1(g)

x
Usama El-Ayaan

Transition Metal Complexes

Usama El-Ayaan

Housecroft and Sharpe, p. 20

Metal d orbitals octahedral metal complexes

M = metal L = ligand

t2g orbitals point between the ligands symmetry

Usama El-Ayaan

eg orbitals point at the ligands symmetry

Housecroft and Sharpe, p. 453

UV-visible spectra of transition metal complexes

Transition metal complexes commonly exhibit UV-visible spectra containing both weak d-d ( < 100) and strong charge-transfer ( > 1000) bands which are characteristic of the nature of both the metal and the ligand(s)

Usama El-Ayaan

Shriver, Langford & Atkins (2nd ed), p. 582

Selection Rules
In electronic spectroscopy there are three selection rules which determine whether or not transitions are formally allowed: 1. Spin selection rule: S = 0 allowed transitions: singlet singlet or triplet triplet forbidden transitions: singlet triplet or triplet singlet Changes in spin multiplicity are forbidden

Usama El-Ayaan

Selection rules
2.

Transition metal complexes get around this rule through M-L vibrations, which temporarily removes the center of symmetry

Laporte selection rule: there must be a change in the parity (symmetry) of the complex Laporte-allowed transitions: g u Laporte-forbidden transitions: g g or

uu

g stands for gerade compound with a center of symmetry u stands for ungerade compound without a center of symmetry
3. Selection rule of = 1 ( is the azimuthal or orbital quantum number, where = 0 (s orbital), 1 (p orbital), 2 (d orbital), etc.) allowed transitions: s p, p d, d f, etc. forbidden transitions: s s, d d, p f, etc.
Usama El-Ayaan

Crystal field theory d orbitals split into two sets

eg t2g

Usama El-Ayaan

Housecroft and Sharpe, p. 455

Crystal Field Splitting

To promote an electron from the lower d orbital to the higher d orbital Usama crystal requires energy equal to oct, the El-Ayaan field splitting energy
Housecroft and Sharpe, p. 456

Spectrochemical Series
Spectrochemical Series (the effect of the ligand set on the magnitude of o) I- < Br- < Cl- < F- < O2- < OH- < H2O < NH3 < NO2- < CN- < PR3 < CO -donor ligands -donor ligands increase the energy of the t2g orbitals -acceptor ligands decrease the energy of the t2g orbitals
Usama El-Ayaan

Visible spectra of octahedral Ni(II) complexes

[Ni(NH3)6]2+

[Ni(H2O)6]2+

1000

300 nm

Usama El-Ayaan

Housecroft and Sharpe, p. 471

Tanabe-Sugano diagrams

d2
excited states

d3

ground state
Usama El-Ayaan

Shriver, Langford & Atkins

UV-visible spectrum of a Chromium(III) complex

Spin-allowed transitions Quartet Quartet

Spin-forbidden transitions Quartet Doublet

Usama El-Ayaan

Shriver, Langford & Atkins (2nd ed), p. 582

d-d transitions in d3 metal complexes

d3

For a d3 metal ion, such as Cr3+ there is one electron in each of the three t2g orbitals, while the eg orbitals are empty

eg t2g
d-d transition

eg t2g
Usama El-Ayaan

Shriver, Langford & Atkins (2nd ed), p. 594

Excitation of d electrons
z z

Electron goes from the dxy orbital into a dz2 orbital *requires a change in planes (xy to z)

Electron goes from the dxz y orbital into a dz2 orbital *much less relocation of x the electron

Usama El-Ayaan

Shriver, Langford & Atkins (2nd ed), p. 590

Tanabe-Sugano diagram d2 ion

Tanabe-Sugano diagram for a d2 ion, such as V2+ 3T 1g
3T

1g

3T2g

3T

1g(F)

3T1g(P)

3T

1g

3A2g

Usama El-Ayaan

Housecroft and Sharpe, p. 472

Jahn-Teller distortions
When a set of degenerate orbitals are unevenly filled, then a perturbation of the molecular structure will occur so that the degeneracy is removed

e.g. [Ti(H2O)6]3+ d1 electronic configuration

eg dz2 dx2-y2 d t2g

2
dxz, dyz dxy

Usama El-Ayaan

[Ti(H2O)6]3+ visible spectrum

[Ti(H2O)6]3+

600

500

400

, nm

Usama El-Ayaan

Housecroft and Sharpe, p. 456

Visible spectrum of [Mn(H2O)6]2+ (1 M solution)

Mn(H2O)62+ is a high-spin d5 ion (t2g3 eg2) and therefore all d-d transitions are spin-forbidden

All of the transitions have values of << 1, (very weak)

Usama El-Ayaan

Brisdon, p.

Charge-Transfer

Ligand-to-Metal Charge Transfer (LMCT)

Metal-to-Ligand Charge Transfer (MLCT) Charge transfer bands are allowed transitions, with values > 10,000
Usama El-Ayaan

Shriver, Langford & Atkins (2nd ed), p. 595

Ligand-to-Metal Charge Transfer

Occurs with metals in high oxidation states (few d electrons) complexed by ligands which are good electron-donors

O
Manganese(VII) has no d electrons, while the O2- (oxide) ligands donate lone pairs of electrons to form double bonds

Mn O O

Permanganate anion
Usama El-Ayaan

UV-Visible spectrum of MnO4-

L M(t2g) L M(eg)

Usama El-Ayaan

Metal-to-Ligand Charge Transfer (MLCT)

Occurs with metals in low oxidation states (lots of d electrons) complexed by ligands which are good electron-acceptors

Ruthenium(II) has 6 d e-

2,2-bipyridine is a good acceptor ligand

Ru(2,2-bipyridine)32+
Usama El-Ayaan

Housecroft and Sharpe, p. 208

Visible spectrum of Ru(2,2-bipyridine)32+

[Ru(bpy)3]2+

MLCT

max = 452 nm = 14,600 M-1 cm-1

Usama El-Ayaan

Coordination Chemistry Electronic Spectra of Metal Complexes

Usama El-Ayaan

Electronic configurations of multi-electron atoms Russell-Saunders (or LS) coupling

For the multi-electron atom For each 2p electron n = 1; l = 1 ml = -1, 0, +1 ms = 1/2 L = total orbital angular momentum quantum number S = total spin angular momentum quantum number
Spin multiplicity = 2S+1

ML = ml (-L,0,+L) MS = ms (S, S-1, ,0,-S)

ML/MS define microstates and L/S define states (collections of microstates) Groups of microstates with the same energy are called terms
Usama El-Ayaan

before we did:
p2
ML & MS Microstate Table States (S, P, D) Spin multiplicity

Terms 3P, 1D, 1S Ground state term 3P

Usama El-Ayaan

For metal complexes we need to consider d1-d10

d2
3F, 3P, 1G, 1D, 1S

For 3 or more electrons, this is a long tedious process

But luckily this has been tabulated before

Usama El-Ayaan

Transitions between electronic terms will give rise to spectra

Usama El-Ayaan

Selection rules
(determine intensities)
Laporte rule g g forbidden (that is, d-d forbidden) but g u allowed (that is, d-p allowed)

Spin rule Transitions between states of different multiplicities forbidden Transitions between states of same multiplicities allowed

These rules are relaxed by molecular vibrations, and spin-orbit coupling

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Group theory analysis of term splitting

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High Spin Ground States

dn d0 d1 d2 d3 d4 Free ion GS
1S 2D 3F 4F 5D 6S 5D 4F 3F 2D 1S

Oct. complex t2g0eg0 t2g1eg0 t2g2eg0 t2g3eg0 t2g3eg1 t2g3eg2 t2g4eg2 t2g5eg2 t2g6eg2 t2g6eg3 t2g6eg4

Tet complex e0t20 e1t20 e2t20 e2t21 e2t22 e2t23 e3t23 e4t23 e4t24 e4t25 e4t26

An e electron superimposed on a spherical distribution energies reversed because tetrahedral

Holes in d5 and d10, reversing energies relative to d1

d5 d6 d7 d8 d9 d10

Holes: dn = d10-n and neglecting spin dn = d5+n; same splitting but reversed energies because positive. Expect oct d1 and d6 to behave same as tet d4 and d9 Usama El-Ayaan Expect oct d4 and d9 (holes), tet d1 and d6 to be reverse of oct d1

A t2 hole in d5, reversed energies, reversed again relative to octahedral since tet.

d1 d6

d4 d9

Orgel diagram for d1, d4, d6, d9 Eg T2g or T2 Energy

or

T2g or T2 Eg or E d1, d6 tetrahedral d4, d9 octahedral 0 d1, d6 octahedral d4, d9 tetrahedral

ligand field strength

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Orgel diagram for d2, d3, d7, d8 ions

Energy

A2 or A2g T1 or T1g P T1 or T1g T1 or T1g T2 or T2g

T2 or T2g T1 or T1g A2 or A2g d2, d7 tetrahedral 0 d2, d7 octahedral

d3, d8 octahedral Usama El-Ayaan , d8 tetrahedral d3 Ligand field strength (Dq)

d2

3F, 3P, 1G, 1D, 1S

Real complexes

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Tanabe-Sugano diagrams

d2

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Electronic transitions and spectra

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Other configurations
d3 d1 d9

d2

d8

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Other configurations

d3

The limit between high spin and low spin

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Determining o from spectra

d1

d9

One transition allowed of energy o

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Determining o from spectra

mixing

mixing

Lowest energy transition = o

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Ground state mixing

E El-Ayaan Usama (T1gA2g) o

- E (T1gT2g) =

The d5 case

All possible transitions forbidden Very weak signals, faint color

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Some examples of spectra

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Charge transfer spectra

Metal character

LMCT
Ligand character

Ligand character

MLCT
Metal character Much more intense bands
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