Ligand Field Theory continued Spectroscopic Term Symbols Selection Rules Orgel Diagrams Tanabe Sugano Diagrams LMCT,

MLCT Nephelauxetic Effect ESR Magnetic Properties

Octahedral, versus trigonal prismatic d0 and d1 complexes

Some d0 and d1 M prefer trigonal prismatic, D3h, rather than Oh Example: [Ta(Me)6]-, [Zr(Me)6]is trigonal prismatic [Mo(Me)6] and [W(Me)6] distorted prismatic M-C bond: 6e- from M, 6e- from 6CH3 L Oh:a1g2, eg4, t1u6 Net stabilization of E for D3h hence many d0 and1d-organometallic complexes are trigonal prismatic not octahedral

Electronic Spectra of Transition Metal Complexes

Absorption band of complex: max position of peak max = Amax/c x l (dm3 mol-1 cm-1) max 0-10,000 d1, d4, d6, d9 complexes one abs. band d2, d3, d7, d8 three abs. bands d5 complexes very weak sharp abs.

Color of transition mretal complex is due to d-d transitions 1. Metal centered d-d 2. CT, charge transfer ML or L M More intense bands =c 1/ =

Absorption of photon in 10-18 s molecular vibrations, rotations much slower breadth of abs. is due to range (many) vibrational and rotational states

different microstates arising from different configuration are Spectroscopic Term Symbols

Spectroscopic Term Symbols

microstates: number of different ways ecan be placed in a given set of orbital sites e.g., p2
or ml 1 0 -1 1 0 -1 or 1 0 -1

Etc.there are 15 different ways to put 2 electrons in 3 p orbitals It is clear that E (ML = 2) > E (ML = 1)

Spectroscopic Term Symbols

n! # microstates = -------e! h!
where n = max # electrons in sublevel (sum of e + h) e = #e- in case study h = # "holes" in case study a site (hole is not occupied by an e-) e.g., d3 : n = 10, e = 3, h = 7

. . .

ML=mli =ml1 + ml2..

MS = ms = ms1 +ms2

Well look at ns2, ns1ns1, and p2 on next slide!

Are other states possible?

Analogous to: l =0 1 2 3 s p d f L=

0 1 2

2S+1L

Total angluar momentum quantum #: J = L+S, L+S-1, L+S-2.l L-S l

For s, F l = 0, ml = 0; for p l =1, ml = 1, 0, -1; ML = ml o r Any other terms?

p2

Largest ML=1+1 = 2 L=2, D; S=0, 2S+1 = 1 1D (2L+1)(2S+1) = 5 states

L=1, S=1; 3P (2L+1)(2S+1) = 9

L=0, S=0; 1S (2L+1)(2S+1) = 1

Highest multiplicity: 2S+1

2S+1 = 4

2S+1= 6

d2 Case
10! 9*10 #microstates = ---------- = ---------- = 45 2!*8! 2

Experimentally determined ordering of energy states

2S+1L J
Identify the ground term symbol of Fe2+ d6
MS = ms; ML = ml; ML = L, L-1.., -L; MS = S, S-1, -S L = 0, 1, 2, 3 4.. S, P, D, F, G S = 0, , 1, 3/2, 2.. 2S+1 = 1, 2, 3

What is the ground term symbol of the C atom with 2p2 electronic configuration?

Is the ground state energy (symbol) the same for [Fe(H2O)6]3+ and [Fe(CN)6]3-?

Spin and Orbital Contribution to the magnetic moment

EJ-(J+1) =(J+1)/ -spin-orbit coupling constant large only for lanthanides f elements At 300 K, RT, kT 200cm-1

4 3

2J+1 levels; E=gJBB0 gJ is the Lande splitting factor these are E levels of epr spectra h is in the radio frequency range

Selection Rules
Spin selection: S = 0 Change in spin multiplicity is forbidden Laporte selection rules: Allowed transitions: g u Forbidden transitions: g g, u u hence, l = 1 Allowed transitions: s p, p d, d f Forbidden: s s, p p, s d, f f, etc.. d d

So why d-d transitions observed? Spin-forbidden transition becomes allowed by mixing of for example singlet and triplet states

Electronic Spectra of Octahedral Complexes-HS only

Ti(H2O6]3+ d1 ml=2, L=2; S=1/2 Ground state: 2D

E of transition depends on oct characteristic of complex

Orgel Diagrams

For Oh and Td d1, d4, d6, d9 one electronic transition spin allowed

T2g Eg

Cr5+, Fe2+ Mn3+, Cu2+

d0, d5, d10 spherical

Eg T2g

What are the multiplicities? For d1: 2Eg 2T2g The others?

Why a doublet? i.e, why two absorption bands, or two transitions? Can you explain?

3A : t 0 2g 2g

eg2

3T : t 1e 1: 1g 2g g

(dxy)1(dx2-y2)1

Consider the d2 ion 3F (ground state), 3P next lowest state

3 possible transistions: 3T F) 3T 2g 1g
3A 2g

3T : t 1e 1: 2g 2g g

(dxy)1(dz2)1

3T : 1g:

t2g2eg0

(F) 3T1g 3T1g

3T (P) 1g

3A : t 0 2g 2g

eg2

3T : t 1e 1: 1g 2g g

(dxy)1(dx2-y2)1

Consider the d2 ion 3F (ground state), 3P next lowest state

3 possible transistions: 3T F) 3T 2g 1g
3A 2g

3T : t 1e 1: 2g 2g g

(dxy)1(dz2)1

3T : 1g:

t2g2eg0

(F) 3T1g 3T1g

3T (P) 1g

Note shift in E of bands for H2O and NH3 complex [Ni(H2O)6]2+ and [Ni(NH3)6[2+ d8 Oh complexes

Note E and in B A B C are Racah parameters take into account electronic repulsions oct/B = 29 E2/B=40 E2 = 25,600 cm-1 40=25,600/B B = 640 cm-1

Application of Tanabe-Sugano DiagramExample 20.5 [V(H2O)6]3+ d2 complex: Absorptions at: 17,200 cm-1 3T2g 3T1g 25,600 cm-1 3T1g(P) 3T1g Estimate B and oct Important point: from Tanabe-Sugano diagram only approx. oct and B possible Let: E2 = 25,600 cm-1 E1 = 17,200 cm-1 Proceed with trial and error:

E1/B=26.9 cm-1 E1 = 17,200 cm-1 B =640 cm-1 oct/640 = 29 oct = 18,600 cm-1

(E2/B)/(E1/B) = 1.49 When oct/B = 20 (E2/B)/(E1/B)=32/18 = 1.78 oct/B = 30 (E2/B)/(E1/B)=41/28 = 1.46 oct/B = 29 (E2/B)/(E1/B)=40/26.9 = 1.49

d2

d4

d3

d5

Non-crossing Rule: if two states of the same

symmetry are likely to cross as a parameter is changed, they will mix together and avoid crossing
T-S for d3

Look at E and A states of same symmetry in d2 Tanabe Sugano diagram

Absorption band width related/clarified by T-S diagram

d3 Note: 4T2 4A2 lines are not parallel small change in o large change in E of transition

CrCl(NH3)5]2+

Effect of L on E of transitions: Cl- vs NH3

[CrCl(NH3)5]2+

Cr(NH3)6]3+
Oh due to C4v vs more splitting of d states

Ligand to - metal charge transfer transition LMCT in tetraoxoanions, [MO4]nM in high oxidation state, L has non-bonding electrons Tetraoxoanions of high valent M are highly colored due to e L ( O) (e MO is empty) Related to E of transition is correlated with electrochemical series:

oxidation state M MnO4- < TcO4- < ReO47+ CrO4- < MoO4- < WO4VO4- < NbO4- < TaO46+ 5+

Note progression of LMCT absorption bands correlates with ease of reduction of M

Metal-to-ligand transitions MLCT: especially Mn+ n=0

* M
2,2-bipyridine

1,10-phenanthroline

orange

tris(2,2-bipyridyl)ruthenium(II) Excited state from CT has lifetime of microsecond, photochemical redox reagent

Photon driven oxidation system

eRuII*(bpy)3 S2O82-

-MnO2 Catalyst

O2 + 4H+

2H2O SO4- + SO42RuII(bpy)3/RuIII(bpy)3

Eox = 1.4 V

eIllumination was done using 250W industrial light source with UV filtered by Pyrex and IR with a 12 cm path water filter at intensity of 20 mWcm-2.

Transitions of Cr3+ in ruby (Al2-xCrxO3) x ~1-2% CrO6 octahedra Luminescence: material emits radiation after electronic excitation a. fluorescence: no change iIn multiplicity ( =nanosec) b. phosphorescence: excited state undergoes interstate crossing to state of different Multiplicity (slow, = sec) and then undergoes radiative decay When emission is stimulated by 627 nm photons reflecting back and forth between two mirrors, it gows in intensity by many orders of magnitudeprinciple of laser by -Theodore Maiman

t2g2eg1 t2g3; 4T2 4A2 ; 4T1 4A2

Evidence of metal-ligand bonding Nephelauxetic effect (electron cloud expanding): evidence that electrons
are shared between M L pairing energies are less in complex than in corresponding Mn+, and effective size of orbitals increases e- is delocalized over whole molecule, hence e- repulsions minimized
For complexes with common metal ion, the nephelauxetic effect varies as: F- < H2O < en < [ox]2- < [NCS]- < Cl- < [CN]- < Br- < IFor metals: Mn(II) < Ni(II) Co(II) < Mo(II) < Re(IV) < Fe(II) < Ir(III) < Co(III) < Mn(IV) Estimate reduction of e- - e- repulsion in complex

(B0 B)/B0 = hligands x kmetal

~ B/B0 the smaller greater is delocalization B = Racah parameter B0 = inter-electronic repulsion in free Mn+ (g)

d1; e.g., Cr5+

E=h = ge BB0
ge = 2.0023 for free ee = B Bohr magneons B0 = applied magnetic field (H)

in practice, is fixed at ~9GHz and B0 = H is varied to observe Resonance Then g is characteristic of dn

Suppose L has nuclear magnetic moment, I 0 if I = 1 2I+1 levels (I nuclear magnetic moment)

If M with unpaired electron is linked to L with I 0, hyperfine splitting of the esr is observed showing that the orbital occupied by the electron has both M and L character; M-L covalent bonding

me=1; mi=0
Observation of esr hyperfine is further evidence of delocalization of e in complex

Exp: eff =(3kMT/N0 B )1/2 eff = 2.828 (MT)1/2

(spin only = 2 [S(S +1)]1/2

Magnetic Susceptibility

A Gouy balance used to measure magnetic susceptibility of sample; change of apparent weight when magnet is turned on is proportional to magnetic susceptibility, =M/H, which is determined by number of unpaired e-

Magnetic Properties and Crystal Field Strength

Low Spin & High Spin Complexes

diamagnetic low-spin complex

paramagnetic

high-spin complex only electron configurations d4, d5, d6, or d7 can have low or high spin
52

Magnetic interaction