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Coordination Compounds
Backgrounds Why atom combines to form chemical bonds? Octet Rule, Pauli Exclusion Principle, Hunds rule and Aufbau Principle Reason: minimum energy and maximum stability/symmetry.

Why, it essential to learn Coordination Compounds?

Biological systems- e.g. Haemoglobin (Fe-porphyrin, red), Chlorophyll (Mg- porphyrin, green), Vitamins B12 (Co-complex), Cytochromes and Oxydase enzymes (Fe-Cu-complex), metalloenzymes, DNAetc.

Alternatively, adrenaline, citric acid and cortisone complex with metals (e.g. Pb,Cu, Fe, Cr), which gave metal poisoning and EDTA-M complexes used in treating metal poisoning.

[Cu(NH3)4]2+ ion inhibits the growth of fungi and bacteria.

[RhI2(CO)2]- ion is used as a catalyst in the "Monsanto Process" for making acetic acid, the active ingredient in vinegar. Na-EDTA complexes: Soap, beer , mayonnaise. EDTA4- is used to "trap" trace amounts of transition metals that could potentially catalyze the decomposition of the product. Colors on a computer Screen, DVD, CD, camera, electronic goods, etc.

Preparation: (A) Simple salts: NaOH + HCl----------> NaCl + H2O (B) Molecular or Addition Compound: Stoichiometric amounts of two or more

stable compounds join together. E.g. Fe(CN)2.4KCN (Pot. ferrocyanide),

and FeSO4.(NH4)2SO4.6H2O (Mohrs salt), etc. Types of Addn. Compounds: (i) Double salts or Lattice compounds: (ii) Coordination or Complex compounds: M-atom / ion + ligands (atoms, ions, or molecules) bonded Coordination bond. Explanation is complex, because each coordination compound has slightly variable chemical, structural and physical behavior depending on M-ion and ligands.

Ligands (complexing agents): Lewis bases - donor atom. Ligands may be +ve (NO+), -ve (X-) or neutral (NH3). In the case of mixed ligands, complex ions gave isomeric structure and geometric shapes. Bidentate ligands gave optically active isomers. (i) Monodentate Ligands: (ii) Bidentate ligands:

(iii) Ambidentate: more than one donor atoms in the same molecule.
(iv) Polydentate Ligands: Having more than two donating sites.

Some Monodentate Ligands ligand name ligand name

FBrH2O OHCN-

fluoride ion bromide ion

water hydroxide ion cyanide ion

ClINH3 CO SCN-

chloride ion iodide ion

ammonia carbon monoxide thiocyanate ion

Methods of Studying Coordinate compounds

1. 2. Electrical conductivity: depends on concentrations and no. of charges on it. Cryoscopic measurement: freezing point changes of a liquid.

3. Magnetic moment/properties: gave no. of unpaired es.

4. Dipole moment: structural information for non-ionic complexes. 5. Electronic Spectra (UV-Vis): for energy of orbitals and shape of complex. 6. X-ray study:

Structure of Coordination Compounds

The arrangement of ligands determine their structure, physical and chemical properties e.g. [CoCl4]2- structure might be: a. Sq. planar-ligands present at the corner of a square

b. Th-ligands present at the corner of Th

c. Something else? Experimentally found Th

1. Werners Coordination Theory (1893)

Alfred Werner (1866-1919)

1893, age 26: Coordination theory

Nobel prize for Chemistry, 1913 Addition of 6 mol NH3 to CoCl3(aq) Conductivity studies Precipitation with AgNO3

NH 3 Co NH 3 NH 3

Cl NH 3 Cl

Cl attached to NH3 may be dissociated

NH 3

NH 3

Cl

Compound CoCl3.6NH3

Moles of ions 4

Moles of AgCl(s) 3

CoCl3.5NH3
CoCl3.4NH3 CoCl3.3NH3

3
2 0

2
1 0

Proposed six ammonia molecules to covalently bond to Co3+

Compound
[Co(NH3)6]Cl3 [Co(NH3)5Cl]Cl2 [Co(NH3)4Cl2]Cl [Co(NH3)3Cl3]

Moles of ions
4 3 2 0

Moles of AgCl(s)
3 2 1 0

Coordination compounds structure:

NH3 H3N H3N NH3 Co NH3 NH3 3+

3Cl (counter-ion)

ligand (coordination sphere)

H N H H

M N forms a coordinate covalent bond to the metal

(i) 1o Valency: Ionizable bonds, (ii) 2o Valency: Non-Ionizable bonds e.g.[Co(NH3)6]Cl3 Generally, CN varies from 1-12. However, 2, 4 and 6 are the most common. CN=2 linear structure CN=4 Sq. planar or Th structure CN=6 Octahedral structure

Why Transition metals form Coordination Complexes?

Sidgwick (EAN rule)- Because TM has vacant d-orbitals, which can accommodate electron pairs to gain stability like next noble gas configuration.

e.g.,K4[Fe(CN)6], EAN=36(Kr);
[Cu(CN)4]-3, EAN=36(Kr); [Ni(CO)4], EAN=36(Kr); [PtCl6]-2, EAN=86(Rn). Exceptions: [Fe(CN)6]-3, EAN=35; [Cr(NH3)6]+3, EAN=33

Role of d-orbitals in the Complex formation:

d-orbitals shape and degeneracy: In case of isolated gaseous and free

metal ion all the five d-orbitals are degenerate. These orbitals are
oriented in space as shown below:

Shape of d-Orbitals

Shape of d-Orbitals

Bonding in TM Complexes
Theories for Metal to Ligand bonding in complexes: Valence bond Theory (L. Pauling, 1930) A complex involves reaction between Lewis bases (Ls) and a Lewis acid (M or Mion) through coordinate covalent or dative bond. Assumptions: 1. Central metal atom or ion have a number of empty s, p, and d orbitals. On hybridization, gave hybrid orbitals. These are vacant, equivalent in energy

and have definite geometry.

2. The ligands have at least one -orbital containing a lone pair of electrons. 3. Hybrid orbitals of the metal atom or ion overlap with the filled -orbitals of

the ligands to form ligandmetal -bond.

This coordinate bond is a special type of covalent bond shows the characteristics of both the overlapping orbitals and Polar in nature due to donation. Pauling measured magnetic moment to find out the number of unpaired electrons in a complex and the geometries of the complex ions having the central metal ion with configurations d1 to d9.

Metal or metal ion: Lewis acid Ligand: Lewis base Hybridization of s, p, d orbitals results:

C.N. 4 4 5 6

Geometry tetrahedral square planar trigonal bipyramidal octahedral

Hybrids sp3 dsp2 dsp3 or sp3d d2sp3 or sp3d2

Example 1: [CoF6]3 Co [Ar] 3d 7 4s2 Co3+ [Ar] 3d 6

3d

4s

4p 4sp3d2
octahedral

4d

complex is paramagnetic

Example 2: [Co(NH3)6]3+ Co [Ar] 3d7 4s2 Co3+ [Ar] 3d6

3d

4s d2sp3
octahedral

4p

4d

complex is diamagnetic

Limitations of VBT: 1. (a) Oh (d2sp3 or sp3d2), tetrahedral (sp3) and square planar (dsp2) complexes of d1(1 unpaired electrons for Oh, Th or Sq. planar), d2 (2

unpaired electrons for Oh, Th or Sq. planar), d3 (3 unpaired electrons for

Oh, Th or Sq. planar) and d9 ion same as d1 and hence cannot be distinguished from each other merely on the basis of the number of unpaired electrons (b) Outer-orbital Oh and Th complexes of all the ions viz. d1 - d9 which have the same number of unpaired electrons cannot be distinguished from each other.

2. Color and magnetic moments of complexes are due to d-orbital electrons.

There must be a quantitative connection between spectra and magnetic moment. This is not revealed in VBT and consequently magnetic and

spectral properties could not be explained by this theory.

3. VBT does not explain the behavior of complexes having d8 ion (e.g. Ni+2, Pb+2, Au+3, etc.) in forming 5-coordinated complexes. Also, VBT prefers

only square planar geometry of complexes not Th or trigonal bipyramidal.

4. The metal ion has much importance while ligand is not properly stressed. 5. VBT cannot explain reaction rates and mechanism of reactions.

A ruby and an emerald (No you cant have them ..).

An artists paint pigment shop in Venice been around since the 1600s ...

Why TM compounds (mainly oxides and sulfides) and complexes have characteristic colors e.g. Cr3+ is green, Co3+ blue, CdS is yellow, HgS orange red, etc...? What is the connection between color and electronic structure ?

2. Crystal Field Theory (CFT) and their Historical Background (H. Bethe, L. Orgel and V. Bleck, 1935)
Mainly applied for ionic crystals. The bonding between the metal atom/ion and the ligands (vely point charge or point charge for anionic Ls and point dipole/dipole for neutral molecules). This explain the d-orbitals splitting into groups as a result of electrostatic

interactions. CFT is very useful to understand, interpret and predict

the magnetic behavior, colors and some structures of coordination complexes.

Bethe et al. investigated, how the strength of a crystal field affect the electronic levels of the gaseous metal atoms/ions. First time, C.F. theory was developed by considering two compounds: MnIIO, and CuICl.

How does we describe and characterize the bonding between M ion and ligands in terms of this electronic theory?

Crystal field around metal s-, p- & d-orbitals and splitting of

d-orbitals in Oh:
Basic concept: purely electrostatic interaction between M+n Ls (bonding attraction) and d-es repel Ls electrons, but unequal that causes splitting of d-orbitals. i. Spherical field: s-, p- and d-orbitals degenerate (remain unchanged). ii. Unsymmetrical field: What will happen? Three interactions are possible between the ligand field with the metallic atom: (i) Ligand field with s orbital (ii) Ligand field with p orbital (iii) Ligand field with d orbital

CFT emphasizes the electrostatic attraction of the chemical bond in a complex of the metallic ion (0/+ve ox. state) with the electrons (-ve ox. state) coming from the ligands.

Bonding in, and Electronic Structure of, Transition Metal Complexes

t2g-orbitals (stabilize) eg-orbitals (destabilize)

The energy difference between eg and t2g-orbitals in the crystal field is known as crystal field splitting (CFS), 10Dq or o. At hypothetical degenerate d-orbitals, no splitting state assumed called Barycenter, CFSE =0. From conservation of energy states t2g orbitals lie at -0.4o and the eg orbitals lie at +0.6o. (CFSEoh= -0.4nt2g + 0.6neg), (n= no. of electrons) Pairing energy? CFSEoh= -0.4nt2g + 0.6neg + mP (m= no. of paired es)

Crystal field splitting diagrams

(i) Octahedral complex: lamda = hc/o

eg

t2g

crystal field stabilization energy (CFSE)

Summary:

CFSE in Oh complexes:
The stability depends upon o and spin pairing energy (P).

Importance of d-orbitals splitting

In octahedral complex, for example d1 complex: electrons place themselves at

t2g orbital which is at the energy level o less than the energy level of d orbital
which does not undergo splitting. The additional stabilization caused by the splitting of d orbital is known as the crystal field stabilization energy (CFSE). Every electron in the t2g orbital set contribute -o for (CFSE). However, electrons in the eg orbital set resides at the higher energy level from d orbital which does not undergo splitting and every electron contributes o to CFSE.

CFSE importance: d2
CFSE = +ve, unfavorable CFSE = 0 (no change in stability) CFSE = -ve (gain stability)

d3

How is a d4 configuration distributed?

CFSE = [-0.4xn1+0.6xn2] o+mP

However, it is highly unfavorable condition due to the greatest loss of

exchange energy. In high-spin ([FeBr6]3), CFSE = 3 x 2/5 o - 2 x 3/5 o

= 0. The stabilization generated by the electrons in the t2g orbitals is canceled out by the destabilizing effect of the electrons in the eg orbitals. d6- CFSE = -2.4o (LS) and if consider pairing energy (P), 2.4o- 3P. CFSE = -0.4o (HS) and 0.4o-P. d7- CFSE = -1.8o (LS) and 1.8o3P & -0.8o(HS) and 0.8o-2P. Similarly,d8, d9 and d10..

Crystal Field stabilization is applicable to metal complexes of all

geometries, inluding square-planar (d8 complexes) having very large CFSE.

Example 1: For Mn3+ ion, the electron pairing energy, P is about 28000 cm-1. o values for the complexes [Mn(H2O)6]3+ and [Mn(CN)6]3- are 21000 cm-1 and 38500 cm-1 respectively. Do these complexes have

HS or LS configuration? Also write down the configurations

corresponding to these states? Example 2: Give the number of unpaired electrons for the [Fe(CN)6]4and [Fe(CN)6]3- complexes.

High-spin (HS-) and low-spin (LS-) Oh complexes Ligands cause large for d-orbitals are known as strong-field ligands. e.g. CN, NO2-, and CO, produce low-spin complexes and follow Aufbau principle. Conversely, ligands (e.g., I & Br) cause small for d-orbitals are known as weak-field ligands and produce High-spin complexes and follow Hunds rule.

Factors affecting the magnitude of o

1. Oxidation state of the metal ion: e.g., [Co(H2O)6]+3; o=18,600 cm-1 and [Co(H2O)6]+2; o=9300 cm-1 2. Nature of the metal ion: increases (30-50%) from 3d to 4d to 5d in the same oxidation state. 3. Number and geometry of the ligands: e.g., t = - 4/9 o smaller than Oh complexes and so t < P gave HS-complexes.

4. Nature of the ligands: Spectrochemical series (see below).

THE SPECTROCHEMICAL SERIES (Tsuchida 1938)

Based on factors affecting CFSE, DO like:

i. the nature of the metal ion. ii. the metal oxidation state. iii. the arrangement of the ligands around the metal ion. iv. the nature of the ligands surrounding the metal ion. Tsuchida experimentally saw the effect of different metal oxidation state and the ligands in the CFSE determination. The arrangement of metal ions or ligands from higher to lower or vice versa is called

spectrochemical series. e.g.,

A. When the geometry and the ligands are held constant, splitting decreases in the following order: strong-field ions Pt4+ >Ir3+ >Rh3+ >Co3+ >Cr3+ >Fe3+ >Fe2+ >Co2+ >Ni2+ >Mn2+ weak-field ions

B. When the geometry and the metal are held constant, d orbitals
splitting decreases in the following order: weak-field ligands I < Br < S2 < SCN < Cl < NO3 < N3 < F < OH < C2O42 < H2O < NCS < CH3CN < py < NH3 < en < 2,2'-bipyridine < phen < NO2 < PPh3 < CN < CO strong-field ligands

Question: Why do ligands F- and CN- that have negative charges are found in the position of the weak and strong series? (a) For complex that contains M-F bond
(i) Ligands donate electrons to the central metal M through orbital on ligand F. (ii) Electrons from t2g orbitals (originated from the metallic ions) are filled in the anti-bonding *- MO which is at a higher energy level as compared to t2g (iii) The effect is the reduction of .

(b) For a complex which contains M-CN bond

(i) Ligands having high-energy *-MOs, which is empty (e.g., CO, CN and H2C=CH2) (ii) As a result, the density of electrons from central metal M can be donated to the ligands through the back-bonding. (iii) Electrons that are filled in (t2g) orbital are from metal. (iv) The effect is the stabilization of t2g orbitals.

Pairing energy (P) vs. (CFSE) DO

1. If DO < P, weak field; HS, e.g., [Cr(H2O)6]2+ 2. If DO > P, strong field; LS, e.g., [Cr(CN)6]4

3. If DO = P, ???; e.g., d4, d6 & d8.

Distribution of d-es in t2g- & eg-sets either in strong or weak Oh fields are same for d1, d2 & d3 ions. Stronger fields (o >P, d4, d5, d6 & d7 ions) have electrons in t2g (low spin/spin paired and so lower resultant spin value). Weaker fields (o <P, d4, d5, d6 & d7 ions) have in eg electrons (high spin/spin free and so greater resultant spin value). d8, d9 & d10 stronger and weaker fields have same distributions in t2g and eg.

e.g., LS- and HS-Oh complexesexamples dx config. d4 [Cr(H2O)6]2+ [Mn(H2O)6]3+ 23500 28000 13900 21000 P value (cm-1) o value -1 (cm ) spin state CFT predicted HS HS Observed expt. Relative magnitude of o & P o <P o <P

HS HS

d5

[Mn(H2O)6]2+ [Fe(H2O)6]3+

25500 30000

7800 13700

HS HS

HS HS

o <P o <P

d6

[Fe(H2O)6]2+ [Fe(CN)6]4[Co(NH3)6]3+ [CoF6]3-

17600 17600 21000 21000

10400 33000 32000 13000

HS LS LS HS

HS LS LS HS

o <P o >P o >P o <P o <P

d7

[Co(H2O)6]2+

22500

9300

HS

HS

The pairing energy is constant along a period. However, the bigger the period the lower the pairing energy (n = 4 << n=3) so many heavy elements are low spin (Fe versus Os). If the P = 10Dq then the hs/ls determination is dependent on temperature. This complex is low spin at low temp, but changes to high spin at rt. some very interesting materials!

Splitting in Tetrahedral geometry: 4-coordinate complexes (Th &

Sq. planar).The CFSE is low and unable to force electrons to pair-HS
complexes result. 2.What will happen with strong field ligands? Why t = -0.45o?

t2

d-electrons config. in Th- HS and LS-ligand fields: CFSE = 0-(- 6Dq) = 6Dq for d1 system; n= no. of unpaired es.

Weak field (HS-complexes)

dx config.
t2 p e q config. d1 d2 d3 d4 d5 d6 d7 d8 d9 d10 t2 0 e 1 t2 0 e 2 t2 1 e 2 t2 2 e 2 t2 3 e 2 t2 3 e 3 t2 3 e 4 t2 4 e 4 t2 5 e 4 t2 6 e 4 n 1 2 3 4 5 4 3 2 1 0

Strong field (LScomplexes) t2 p e q config. t2 0 e 1 t2 0 e 2 t2 0 e 3 t2 0 e 4 t2 1 e 4 t2 2 e 4 t2 3 e 4 t2 4 e 4 t2 5 e 4 t2 6 e 4 n 1 2 1 0 1 2 3 2 1 0

Squar planar:

DSP

z out condition

Sq. planar

Why sp = 1.3o?

M-ions (d8)-strong ligand field gave Sq. planar (LS) complexes. e.g., [Ni(CN)4]-2, [Pt/PdCl4]-2, [Pt(NH3)4]+2 & [AuCl4]-1 where dx2-y2 remain always unoccupied.

Different Ways of d-d transitions

a) dz2 -----dxy Creates more repulsion

b) dz2 ------dxz Creates less repulsion

Selection Rules for Electronic Spectra of TMs- Complexes

1. The Spin Rule, S = 0 (Allowed)- i.e., (electronic transition occurs from the ground state to the next excited states with the same multiplicity or no change in spin).
allowed transitions: singlet - singlet or triplet -- triplet forbidden transitions: singlet -- triplet or triplet -- singlet
Spin-forbidden transitions Change in the spin state of the molecule are forbidden Strongly obeyed in lighter atoms Relaxed by effects that make spin a poor quantum number (heavy atoms)

For example,(d5) [Mn(H2O)6]+2 d-d transition forbidden-colorless/pale flesh.

2. The Orbital Rule (Laporte), l = +/- 1, +/-2 (Allowed)- there must be a change in the parity (symmetry) of the complex.

s2---s1p1 l = +1 (Laporte allowed, =5000-10000 unit), d---d, l = 0 (Laporte forbidden, =5-101 unit). In TM-L complexes, due to d & p

orbitals mixing (not pure d-d) in nature, e.g., (e.g.,Th- [MnBr4]-2) and
distorted Oh complexes [Co(NH3)5Cl]+2-colored. No d & p orbitals mixing in Oh [Co(NH3)6]+3 & [Cu(H2O)6]+2 colorless/fade.

Expected intensities of electronic transitions

Transition type Spin forbidden, Laporte forbidden Spin allowed (Oh complex), Laporte forbidden Spin allowed (Th complex), Laporte partially allowed by d-p mixing Spin allowed, Laporte allowed e.g. charge transfer bands Example [Mn(H2O)6]2+ [Ti(H2O)6]3+ value of m2 mol-1 0.1 1

[CoCl4]2-

50

[TiCl6]2- or MnO4-

1000

For M2+ complexes, expect = 7500 - 12500 cm-1 or = 800 - 1350 nm. For M3+ complexes, expect = 14000 - 25000 cm-1 or = 400 - 720 nm.

Relaxation of the Laporte Rules can occur through:

a) Spin-Orbit coupling - gives weak spin forbidden bands;

b) Vibronic coupling - an oh complex may allowed vibrations when molecule is asymmetric so absorption of light is possible. c) -acceptor & -donor ligands mix with d-orbitals (geometry relaxation during transition) so transitions are no longer purely d-d.

Applications of C.F. Theory

1. Ionic Radii: MXs (Oh)
1.0

Sc+2-unstable X

Ionic radii

0.6 3d=0

CFSE=-12Dq

3d=10

+2 Ca+2 Sc+2 Ti+2 V+2 Cr+2 Mn+2 Fe+2 Co+2 Ni+2 Cu+2 Zn no. of 3d-electrons

(Oh ionic radii of M+2 for 1st row transition metals)

CFSE=0 for d0, d5(HS) and d10 systems For M+3 ions trends and explanations are same. CFSE= - ve (more ve values, more stable complexes)

1st row TM, ionic radii of M+2-ions, e.g., metals halides (MX2, X= F, Cl, Br, I, Oh shape). Theoretical and Experimental values are same for Ca+2 (d0), Mn+2 (d5, HS), Zn+2 (d10), CFSE = 0, Two extreme cases, V2+ (d3) & Ni2+ (d8) in a weak ligand fields (Xs), CFSE = 1.2o, others (d2, d4, d7 & d9), CFSE = 0.6 - 0.8o. Why? F->Cl->Br->I- in electronegativity, What will be the ionic radii trend in 1st TM?

Strong ligands? Ionic radii decreases for the strong field case until the
t2g6 config. is reached, due to increasing nuclear charge and poor shielding by t2g d-electrons. At this point the next electron enters the egorbital directed at the ligands, repelling them and causing an increase in the effective radius of the metal-ligand.

Hydration enthalpy/stability of complexes/L.E.

F- >> Cl- > Br- > Iexperimental values of CFSE 500 x x x x Calculated values of CFSE x x
x

1000

experimental values of CFSE x

heats of hydration (kcal/mol)

heats of hydration (kcal/mol)

450

900
x x

x Calculated values of CFSE

400

800

350 Ca+2 Sc
+2 +2 Ti+2 V+2 Cr+2 Mn+2 Fe+2 Co+2 Ni+2 Cu+2 Zn

700
+3 Ca+2 Sc+3 Ti+3 V+3 Cr+3 Mn+3 Fe+3 Co+3 Ni+3 Cu+3 Zn

(Hydration enthalpy of M+2 and M+3 for 1st row TMs in Oh complexes)

CFSE value for Heat of hydration of M+2 and M+3-ions of 1st-row TM, a similar trends is found for the lattice energy vs TM-ions. Higher the heat of hydration or lattice energy-more stable compounds (CFSE?).

Here, the experimental values increasing irregularly, maxima at V+2 (d3 ion) and Ni+2 (d8) and minima at Ca+2(d0 ion), Mn+2 (d5) and Zn+2 (d10). The unexpected maxima and minima can be explained on the basis of CFSE concept. [M(H2O)6]+2 are high-spin Oh complexes and for highspin complexes, CFSE is minimum (zero) for d0 (Ca+2), d5 (Mn+2) and d10 (Zn+2) ions and maximum (=1.2 o) for d3 (V+2) and d8 (Ni+2) ions. In toto, Ca+2/+3 to Zn+2/+3 ionic radii decrease-hydration energy increase.

Color of Complexes
The bright colors exhibited by many coordination compounds can be explained by C.F. Theory. When white light is allowed to fall on a complex, the following things may occur: i. The complex may absorbed the whole white light. Thus complex appears black. ii. The complex may reflect (or transmit) the whole light. In this case it

appears white.
iii. The complex may absorb some of it and may reflect (or transmit) the remaining light. In this case the complex has some color, i.e. it is colored. The absorption of light by the complexes takes place in the visible region of the spectrum (4000 to 7000 wavelength).

The color of the absorbed light is different from that of the transmitted light called complementary color. The relation between the colors of the absorbed and reflected light is as below:

High---------------------------------decreasing energy-----------------------------------------Low Color absorbed of absorbed the Violet 4000 Blue 4350 Green -blue 4800 Bluegreen 4900 Green 5000 Yellowgreen 5600 Yellow 5800 Orange 5900 Red 60507000

Low -----------------------------increasing wavelength--------------------------------------------High Color transmitted (color of the complex Yellowgreen Yellow Orange Red Purple Violet Blue Green Bluegreen

[Cu(H2O)4]2+ ions--hydrated cupric sulphate (blue), [Ti(H2O)6]3+ ions (purple)

The complex ions absorb light in the IR (> 7000 ) or UV (< 4000 )
are colorless, e.g. (i) anhydrous cupric sulphate is colorless, IR region. (ii) [Cu(CN)4]2- ion UV region, colorless. Wave no. () = 1/ (cm) =1/ x 10-8 cm =x cm-1 (1 cm-1=2.85 x 10-3 kcal/mole or 350 cm-1 = 1.0 kcal/mole). Note: Rarely, the energy of the photon absorbed corresponds exactly to the size of the gap ; Other factors (such as electron-electron

repulsion and Jahn-Teller effects) that also affect the energy

difference between the ground and excited states.

 = 5000
Molar absorptance

(Visible absorption spectrum of [Ti(H2O)6]3+ ion. Peak of the curve shows the maximum absorption)
30000 20000 (cm-1) 10000

Visible absorption spectrum of a complex ion is useful in predicting the

color of the complex. e. g., [Ti(H2O)6]3+ ion shows absorption maxima at a wavelength of about - 5000. = 1/ (in cm). 5000- green color absorbed. Transmitted light is purple (o, E= 57 kcal/mole), corresponding to t2g1 eg0------t2g0 eg1 called d-d or ligand field transition.

Magnetism of Complexes
dx config. Ions n s exp

d1 d2 d3 d4 d5 d6 d7 d8 d9

Ti+3 Ti+2, V+2 V+2 Cr+3 Cr+2 Mn+3 Mn+2 Fe+3 Fe+2 Co+3 Co+2 Ni+2 Cu+2

1 2 3 4 5 4 3 2 1

1.73 2.83 3.87 4.90 5.92 4.90 3.87 2.83 1.73

1.73-1.85 2.75-2.85 3.80-3.90 4.75-4.90 5.65-6.10 5.10-5.70 4.30-5.20 2.80-4.00 1.70-2.20

s = n(n+2) BM. (BM- Bohr Magneton). Spin only formula is valid in 1st row TMs. [CoCl4]2- & [MnF4]2- gave 1.73 and 5.9 BM respectively, predict the geometry?

Magnetic property of coordination compounds gave:

Unpaired electrons in d-orbitals and the magnetic moment Transition metal complexes are Paramagnetic or Diamagnetic. The crystal field splitting diagram as well as strong or weak field ligands and the way of the ligand field splitting parameter changes with the nature and oxidation state of a transition element (HS and LS complexes).

Distortion of Oh Complexes
In Oh-complexes, when all ligand electron clouds and metal ion are at the same length called regular (i.e. symmetrical) Oh complexes. Conversely, unequal length Oh are called distorted Oh complexes. The change in shape is called distortion. Distorted in Oh complexes may be of the following three types:

(i) Diagonally distorted Oh complexes: Distortion of a regular Oh along

two-fold axis. (ii) Trigonally distorted Oh complexes: Distortion along a three-fold axis. (iii) Tetragonally distorted Oh complexes: Distortion along four-fold axis.

For example: (a) Elongation along z-axis (Z-out condition): two long bonds (z-axis) and four short bonds (xy plane). e.g.,

i. CuCl2: four at 2.30 and two at 2.95 bond length.

ii. CuF2: four at 1.93 and two at 2.27 bond length. iii. LS-Oh complexes of Ni+2, Pd+2 and Pt+2 (all d8 ions) - strong distortion gave square planar geometry. (b) Compression along z-axis (Z-in condition): two short bonds (z axis) and four long bonds (xy plane). e.g., (i) K2CuF4: two at 1.95 and four at 2.08 . (ii) FeF2: two at 1.99 and four at 3.12 .

(conditions (a) & (b) gave Tetragonal distortion geometry) shown below:

eg

x2-y2
1

x2-y2
x2-y2 z2

t2g + eg
+6Dq 10Dq -4Dq

xy
+0.4 t
t

yz xz t2g
t = 0.45 o

xy

z2
2

sp

z2
3

xy yz xz
xy yz xz t2g Octahedral

xy yz xz x2-y2 z2 degenerate d-orbitals on Mn+

-0.6

yz xz Sq. Planar

Tetragonal

x2-y2 z2 eg Tetrahedral

(z-elongation)

HS-Oh complexes: weak ligand field

LS-Oh complexes: strong ligand field Distribution of es- in t2g and eg-orbitals t2g0(sym)-eg0(sym) t2g1(unsym)-eg0(sym) t2g2(unsym)-eg0(sym) t2g3(sym)-eg0(sym) t2g4(unsym)-eg0(sym) t2g5(unsym)-eg0(sym) t2g6(sym)-eg0(sym) t2g6(sym)-eg1(unsym) Predicted Distortion No distor. Slight D Slight D No distor. Slight D Slight D No distor. Strong D

No

of

electrons

Distribution of es- in t2g and egorbitals t2g0(sym)-eg0(sym) t2g1(unsym)-eg0(sym) t2g2(unsym)-eg0(sym) t2g3(sym)-eg0(sym) t2g3(sym)-eg1(unsym) t2g3(sym)-eg2(sym) t2g4(unsym)-eg2(sym) t2g5(unsym)-eg2(sym)

Predicted Distortion No distor. Slight D Slight D No distor. Strong D No distor. Slight D Slight D

d0 d1 d2 d3 d4 d5 d6 d7

d8

t2g6(sym)-eg2(sym)

No distor.

t2g6(sym)-eg2(unsym)

Strong Distor.
leads planar sq.

d9 d10

t2g6(sym)-eg3(unsym) t2g6(sym)-eg4(sym)

Strong D No distor.

t2g6(sym)-eg3(unsym) t2g6(sym)-eg4(sym)

Strong D No distor.

No Distortion Condition: Both t2g and eg-sets as symmetrical orbitals lead to perfectly symmetrical (regular) Oh complexes.

Condition for slight Distortion: d-orbitals of Oh complexes have t2gorbitals as unsym. orbitals gave slight distortion in the complex, because they do not come directly in front of the ligands approaching for metal ion. Only slight distortions from the regular Oh was observed. However, not experimentally detected in Oh.

Condition for strong Distortion: eg orbitals pointing directly towards the

ligands are unsym.(i.e. 1, 3 & 2 es) (only in LS-complexes), gave strong distortions, leading to tetragonal and even to sq. planar complexes.

Jahn-Teller Effect/ Theorem (1937): Explain, why certain complexes undergo distortion? (i.e. Oh ---tetragonal) Statement any non-linear molecular system possessing degenerate electronic state will be unstable and will undergo distortion to form a system of lower symmetry and lower energy and thus will remove

degeneracy. Jahn-Teller distortion is automatic for the non-linear

molecular systems. It does not predict the nature or its magnitude of distortion. However, always occurs in a manner which decrease in the energy of the system. Symmetrical: t2g-orbitals: t2g0, t2g3, t2g6; eg-orbitals: eg0, eg4 and eg2 in HScomplexes (dx2-y2)1 (dz2)1 (No J-T distortion observed).

Unsymmetrical: t2g-orbitals: t2g1, t2g2, t2g4, t2g5; eg-orbitals: eg1, eg3 and eg2 in LScomplexes (dx2-y2)0 (dz2)2 (J-T distortion observed). Cause of distortion with some complexes: e.g., (i) d4 ion (HS): two possible config. of es in t2g- & eg-orbitals: 1. t2g3 dz21 dx2-y20 2. t2g3 dz20 dx2-y21 case 1, M+-L interaction along the z-axis is more than along the x- and y-axes, leads to a larger inter-ionic distance (called z out condition or z-elongation).

(ii) d9 ion (Cu2+ complex) e.g., aq. soln. of [Cu(NH3)4]2+ - a large tetragonal
distortion (sq. planar complex). M-ion has config. t2g6eg3 in both the fields (LS & HS). The two possible arrangements of electrons in t2g- and eg-orbitals are: 1. t2g6 dz22 dx2-y21 and 2. t2g6 dz21 dx2-y22 Thus, a large distortion/Asymmetry is only due to eg incomplete orbitals.

Cause of Distortion: Strong distortion mainly due to repulsion of M-Ls

electrons in eg-orbitals. E.g., in d4 ion (HS) and d9 ion (Cu+2 ion, LS & HS),
Case 1. d-electron charge density is higher in z direction than x and y. Thus dz2 orbital (half filled (d4) & completely filled(d9)) offers greater shielding of the Cu+2 nucleus than the half filled dx2-y2 orbital. Same time, the ligands on the x- and y-axes experience a higher effective nuclear charge. So, the ligands on the x- and y-axes are drawn in closer to the Cu+2 nucleus and those on the z-axis move further out (called z

out condition or z-elongation).

Thus, the Oh-complex will distorted to tetragonal geometry which is elongated along z direction and compressed along x and y directions.

Since the distortion to tetragonal geometry is automatic (without

supplying energy from outside), the overall energy of the unsplit eg orbitals are zero. Therefore, sum of energy after splitting must be zero. Conclusion: whenever there are more electrons in dz2 orbital than in dx2y2

orbital (Oh complex) of any M-ion distortion follow the above rule and

maintain the centre of gravity rule.

Consider configuration 2: (dz2)1 (dx2-y2)2 t2g6, explanation for this observation is exactly the same. However, dx2-y2 will be higher in energy. The resulting distortion will be called Z-in condition. How then to decide which of the two possible Oh distortion config.(1. (dz2)2 (dx2-y2)1 t2g6 and 2. t2g6 (dz2)1 (dx2-y2)2 ) would yield the more stable complex? CFT offers no way of deciding it. Experimental results, however, show that it is Z out condition Oh distortion configuration with two long and

four short bonds which is more stable. There is no theoretical

explanation for the instability of structure corresponding to Z-in condition having four long and two short bonds.

t2g1 configuration in Oh complexes: Single electron can occupy any t2g orbitals. If the electron is in dxy orbital, it would screen the M-ion nucleus more effectively in xy plane than in xz & yz planes. This would reduce the attraction between M-L in xy plane. So, the Oh geometry of the complex would get distorted by the elongation of the M-L bonds in xy plane. Repulsion increased and energy decreased in the same plane as compared to yz & xz planes. On the other hand, if the electron is present in either dxz or dyz orbital, it will screen M-ion nucleus more effectively in the xz and yz planes compared to the xy plane, and decrease attraction between M-L along the z axis. Thus, the bonds along the z direction elongated and get distorted to tetragonal geometry.

The energies of both dxy and dx2-y2 orbitals alter in a similar manner due to distortion of Oh geometry by Jahn-Tellar effect. The change in energies of these orbitals will again obey the centre of gravity rule. The J-T effect shown by t2g orbitals is much weaker than eg orbitals. Because in t2g orbitals the charge density lie in between the x, y and z directions, while in

eg orbitals, the charge density lie directly in the directions along which the
ligands are placed. Thus, an electron in any of the t2g orbitals would shield the positive charge of

M-ion much less effectively in the x, y and z directions, i.e. along the directions
of the ligands than the electron placed in any of the eg orbitals.

The magnitude of J-T effect is related to the screening of the nuclear charge of the M-ion by the d electrons in the directions of the ligands. It is smaller in Oh complexes with ground state configurations t2g1, t2g2, t2g4 and t2g5 than in ground state configurations t2g6 eg1, t2g6 eg3, t2g3 eg1, etc. In fact, it has not been possible to detect J-T effect in Oh complexes of M-ions with ground state configuration t2g1, t2g2, t2g4 and t2g5 (except from indirect

spectroscopic evidence) because the magnitude of the effect is comparatively

very small and these complexes get little bid more stabilized due to J-T effect.

Jahn-Teller effect on Electronic spectra of Complexes

Electronic absorption bands in the spectra of coordination complexes

are associated with d-d transitions (t2g --- eg ). For example,

[Ti(H2O)6]3+- Oh complex, (d1 system), absorbs around = 5000 . This should give rise to a single symmetrical absorption band. But is not so, absorption band is unsymmetrical, which result of overlapping of more than one absorption bands. This can be accounted for on the basis of JT effect as follows:

% ABSORPTION

(Unsymmetrical absorption band observed in the spectrum of [Ti(H2O)6]+3).

1000 1500 2000 (cm-1) 2500 3000

Suppose, electron is in dxy orbital (slightly stable complex). The complex distorted to tetragonal geometry in which the Ti-OH2 bonds along z axis are shorter than x and y axes. The energy of dxy orbital gets lower than dxz and dyz orbitals and energy gap 2 between dxy and (dxz, dyz) is much smaller than the average width of an electronic absorption band (2 - neither account for absorption of EMR (Vis- region) nor asymmetry in the electronic absorption band of [Ti(H2O)6]+3).

Thus, dxy electron on excitation may occupy either (i) dx2-y2 orbital or (ii) dz2 orbital. If the electron occupies dx2-y2 orbital in the excited state, charge polarized more in the xy plane and if in dz2 orbital it will be along the z direction. This results in two electronic sets in the excited state having different energy.
dz2

dx2-y2
E

D E1

D E2 dxz, dyz dxy

(Splitting of the excited state energy levels due to J-T effect in [Ti(H2O)6]+3 in the distorted geometry making possible two electronic transitions).

Lowering of the symmetry of [Ti(H2O)6]+3 from Oh to tetragonal due to J-

T effect, splits the excited state and makes possible two electronic
transitions or electronic jumps, viz. dxy1 dx2-y21 and dxy1 dz21, which should give rise to two absorption bands. Since the energy difference 2 between dxy and dxz, dyz is very small, the population difference between dxy and dxz, dyz levels is also very small. Therefore, the ground state of [Ti(H2O)6]+3 is often written as t2g1 and transition as t2g1 dx2-y21 and t2g1 dz21.

Conversely, suppose Ti-OH2 bonds along z axis are longer than bonds along x and y directions. i.e., (dxz, dyz)1 ---dz21 (lower energy) than dx2y2 1.

Thus, two transitions; t2g1 dx2-y21 & t2g1 dz21.

The distorted geometry of Ti(H2O)6]+3 obtained by compression of TiOH2 bonds along z axis is stable by 2/3 over its distorted geometry obtained by elongation of Ti-OH2 bonds along z axis. But the difference

2/3 in the energies of the two distorted geometries of Ti(H2O)6]+3 is very

small and the thermal energy available at rt to these complex ions in the distorted geometry is sufficiently enough to allow these ions to change their geometry.

dx2-y2

dz 2 D E1 D E2 dxy dxz, dyz

(Splitting of the excited state energy levels due to J-T effect in [Ti(H2O)6]+3 in the distorted geometry making possible two electronic transitions).

Since E1 (Edx2-y2 - Edxz, dyz) is close to E2 (Edz2 Edxz, dyz) , the two transitions will again give rise to two overlapping bands (unsymmetrical band). Thus, an unsymmetric absorption band will be observed whether the complex ion [Ti(H2O)6]+3 has the distorted geometries and an equilibrium exists between them due to dynamic J-T effect.

Factors determine the geometry of the complex ions:

1. J-T effect favor the distorted Ti(H2O)6]+3 in which dxy (lowest energy). 2. The thermal energy available to the complex tends to equalize the population of ions in the two distorted geometries. Thus, an equilibrium condition between

the populations of the two distorted geometries exists. This is known as

dynamic J-T effect (dynamic J-T effect, energy gap of t2g & eg should be small). 3. In Oh complex, the energy gap between t2g & eg is quite high. The thermal energy available at rt is not enough to influence the population of the ions in any distorted geometries. Hence, J-T effect will solely determine the stable distorted geometry in which the complex will acquire. Such distorted geometry is known as static J-T effect.

Consider, Cu+2: viz. [Cu(H2O)6]+2. Mostly Oh complexes of Cu+2 exhibit

tetragonal distortion because of J-T effect in which Cu-L bonds along z

axis are elongated compared to the bonds in the xy plane.
dx2-y2 eg3 3 2 1 dz 2 t2g6 dxy dxz, dyz

(Possible electronic transition in tetragonal [Cu(H2O)6]+2).

The electronic absorption spectrum of Cu+2: splitting of eg orbitals in Oh Cu+2 complexes gave the energy of the dz2 orbital decreased close to the

energies of dxy & (dxz, dyz) orbitals (J-T effect). Therefore, the energy
required to excite an electron from any one of these orbitals to the partially vacant dx2-y2 orbital is nearly of the same magnitude. Thus, the following three electronic transitions are possible in electronic spectra of [Cu(H2O)6]+2 : (i) Transition from dz2 ---- dx2-y2 orbital by absorbing energy h1. (ii) Transition from dxy ---- dx2-y2 orbital by absorbing energy h2. (iii) Transition from dxz ---- dx2-y2 orbital by absorbing energy h3.

The three transitions of close energy would give rise to three absorption bands at close frequencies 1, 2 and 3 which overlap to give a composite, unsymmetrical absorption band as shown:

% ABSORPTION

5000

10000 (cm-1)

15000

If no J-T distortion, the spectrum would have consisted of a single symmetric band corresponding to the transition t2g6eg3 t2g5eg4. The observed spectrum of the complex explained only on the basis of the JT effect.

Limitations of CFT
(i) CFT considers only the M-ion d-orbitals and gives no consideration to other M-orbitals as s-, p-orbitals or ligand -orbitals. Thus, to explain all the properties of the complexes dependent on the -ligand orbitals will be outside the scope of

CFT. This does not consider the formation of -bonding in complexes.

(ii) CFT is unable to account the relative strength of ligands. It gives no explanation, why H2O is a stronger ligand than OH- in the spectrochemical series (iii) According to CFT, the bond between the M-Ls are purely ionic. It gives no account of the partly covalent nature of the M-ligand bonds and the effects directly dependent on covalently cannot be explained by CFT.

Subject: what is spin multiplicity in spin quantum no.??

In quantum mechanics, spin multiplicity denotes the number of possible quantum states of a system with given principal spin quantum number S. The different states are distinguished by the spin projection quantum number Sz, which can take the values -S, -S+1, ..., S-1, S. Therefore, the multiplicity is 2S+1, where S is the number of singly occupied electrons multipled by the Electron Spin Quantum Number, ms.A system with S=0 has exactly one possible state; it is therefore in a singlet state. A system with S=1/2 is a doublet; S=1 is a triplet, and so on.The most important application is to electrons. A single electron (as in a free radical) has S=1/2; it is therefore always in a doublet state. Two electrons (as in a diradical) can pair up in a singlet or in a triplet state. Normally the singlet is the ground state.For example, oxygen has two singly occupied electrons which could have spin multiplicity of 3. This means that the spins could be up up or up down or down down, total 3 possibilities. Using the formula, Spin Multiplicity of oxygen = 2S+1 = 2(2*1/2)+1 = 3, where S= two singly occupied electrons*ms. (ms always equal to 1/2)

S. R. or transition rule Selection rules have been derived for electronic, vibrational and rotational transitions. To get the selection rules for and , we shift gears, and treat light as an electromagnetic wave, not photons. Also, we consider the reverse process, where an atomic state absorbs energy from incident light. An electron is so small (pointlike, so far as we know today) that it feels at any moment a uniform electric field, and a uniform magnetic field. Classical physics says that magnetic effects are much smaller than electric effects, so we will ignore the former. (In modern parlance, we are ``deriving'' the selection rule for electric dipole transitions, and ignoring magnetic dipole transitions.) The uniform electric field can shove the electron this way or that, but cannot flip it over. So S is unaffected, and hence . On the other hand, if the wavelength of light is short enough, the electric field will be shoving the electron one way in one part of its orbit, and another way for another part, and so may change its orbital angular momentum L. . We've just seen that S doesn't change, so L and J must change the same way. So the selection rules for and must be the same as those for and .