Coordination Compounds

Why atom combines to form chemical bonds?

Octet Rule: Pauli Exclusion Principle, Hunds rule and Aufbau Principle Reason: minimum energy and maximum stability (s- and p-normal salts).

Is it so important to study Coordination Compounds? Importance: Many coordination compounds are found in biological systems. e.g. Haemoglobin (Fe-porphyrin, red), Chlorophyll (Mg- porphyrin, green), Vitamins B12 (Co-complex), Cytochrome and Oxydase enzymes (Fe-Cu-complex).

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 compexes: 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.

Molecular or Addition Compound: Stoichiometric amounts of two or more stable compounds join together. E.g. Fe(CN)2.4KCN (Pot. ferrocyanide), KCl.MgCl2.6H2O(carnallite) and FeSO4.(NH4)2SO4.6H2O(Mohrs salt), etc.

Types of Addn. Compounds:

1. 2. Double salts or Lattice compounds: Coordination or Complex compounds: composed of a metal atom or ion and one or more ligands (atoms, ions, or molecules) that are formally donating electrons to the metal center. Explanation is complex, because each coordination compound has slightly variable chemical, structural and physical behavior depending on metal ion and ligands.

Coordinate covalent bond/Dative bond: A Lewis acid-base reaction in

which neutral molecules or anions bond to a central metal atom (or ion).

Ligands (complexing agents): Lewis bases - contain at least one pair of

electrons to donate to a metal atom or ion. Within a ligand, the atom that is directly bonded to the metal atom/ion is called the 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.

Monodentate Ligands: Lewis bases that donate a single pair of es to a

matal atom. It may be anions (usually) or neutral molecules.

Bidentate ligands: Lewis bases that donate two pairs ("bi") of electrons
to a metal atom. Bidentate ligands are often referred to as chelating ligands ("chelate" is derived from the Greek word for "claw") because they can "grab" a metal atom in two places. A complex that contains a chelating ligand is called a chelate.

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

Some Monodentate Ligands ligand FBrH2O OHCNname fluoride ion bromide ion water hydroxide ion cyanide ion ligand ClINH3 CO SCNname chloride ion iodide ion ammonia carbon monoxide thiocyanate ion

Complex ion: If the coordination complex carries a net charge, the complex
is called a complex ion. Coordination compounds and complex ions are distinct chemical species - their properties and behavior are different from the metal atom

or ion and ligands from which they are composed.

Coordination sphere: a coordination compound or complex consists of the

central metal atom or ion plus its attached ligands. The coordination

sphere is usually enclosed in brackets when written in a formula.

Coordination number: The number of ligands bonded to the metal or M-ion

is called Coordination Number (CN) of the metal and the bonding called Coordination Bond (CB).

Methods of Studying Complexes 1. Electrical conductivity: depends on concentrations and no. of charges on complex. 2. 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 (counterion)

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, coordination number (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 config.

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:

(i) 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:

1.

Valence bond Theory (L. Pauling, 1930)

A complex involves reaction between Lewis bases (Ls) and a Lewis acid (M or M-ion) 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

Example 3: [PtCl4]2, Pt2+ [Xe] 4f 14 5d 8,

5d

6s dsp2
Sq. planar

6p

complex is Diamagnetic

Example 4: [NiCl4]2, Ni2+ [Ar] 3d 8

3d

4s 4sp3

4p

tetrahedral complex is paramagnetic

Example 1. called Outer-orbital Oh complex (Huggin) Example 2. called Inner-orbital Oh complex (Pauling) Outer-orbital Oh complexes also called ionic complexes and inner-orbital complexes as the covalent complexes.

These complexes are also known as spin-free and spin-paired (by Nyholom),
high-spin (HS) and low-spin (LS) (by Orgel).

Some examples:
Inner-orbital complexes: d3-[CrIII(NH3)6]3+; d4-[CrII(CN)6]4-, [MnIII(CN)6]3-; d5[FeIII(CN)6]3-; d6-[FeII(CN)6]4-, [CoIII(NO2)6]3-, [CoIII(H2O)6]3+, [Co(en)3]3+,

[PtIV(NH3)6]4+; d7-[CoII(NO2)6]4-.

Outer-orbital complexes: d3-[CrIII(H2O)6]3+; d4-[CrII(H2O)6]2+,

[MnIII(H2O)6]3+; d5-[MnII(H2O)6]2+, [FeIII(H2O)6]3+, [FeIIIF6]3-; d6[FeII(H2O)6]2+, [FeII(NH3)6]2+; d7-[CoII(H2O)6]2+; d8- [NiII(NH3)6]2+, [NiII(H2O)6]2+; d9-[CuII(NH3)6]2+; d10-[CuI(NH3)6]1+.

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.

2. Crystal Field Theory and their Historical Background

(H. Bethe, L. Orgel and V. Bleck, 1935) The C.F. model mainly applied for ionic crystals and describes the bonding between the metal atom/ion and the ligands (a ve 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 crystalline field affect the electronic levels of the gaseous metal 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 the metal s-, p- and d-orbital (Oh):

Basis: purely electrostatic interaction i. Spherical field: d orbitals degenerate; s- and p-orbital remain unchanged.

ii. Unsymmetrical field: What will happen?

s- and p-orbitals remain degenerate even under Oh ligands field influence. However, d-orbitals split depending on ligands field type. They are:

Diagram for the metal d-orbitals splitting in Oh Crystal Field

The energy difference between eg and t2g-orbitals in the crystal field is known as crystal/ligand field

splitting energy (CFSE), 10Dq or o. At hypothetical

degenerate d-orbitals, no splitting state assumed called Barycenter, E=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

Crystal field splitting diagrams

(i) Octahedral complex:

eg

t2g

crystal field stabilization energy (CFSE)

Pentagonal pyramidal

Summary:

Crystal field stabilization energy (CFSE)

CFSE gave the stability of complex on placing a metal ion in the ligand field generated by a set of ligands. Due to d-orbitals splitting, some of d-orbitals become lower in energy than before with respect to a spherical field known as the barycenter in which all five d-orbitals are degenerate. e.g. Oh complex: CFSE = 0- (-4Dq) = 4Dq (d1-system), d2 = 2 x 4 Dq = 8 Dq; d3 = 12Dq. For d4two possibilities: t2g4 (CFSE = 16Dq) or t2g3 eg1 (CFSE = 6Dq). As a result of splitting, if there are any electrons occupying these orbitals, the metal ion is more stable in the ligand field relative to the barycenter by an amount known as the CFSE. The stability will depend on o and also spin pairing energy (P).

Distribution of electrons o= +ve, unfavorable o= 0 (no change in stability) o= -ve (gain stability)

d2

d3

How is a d4 configuration distributed? CFSE = [-0.4xn1+0.6xn2] o+mP

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]4- and [Fe(CN)6]3- complexes.

d5 e.g., low-spin ([Fe(NO2)6]3) has five electrons in the t2g orbitals. CFSE is 5 x 2/5 o= 2o. However, it is highly unfavorable condition due to the greatest loss of exchange energy. In high-spin ([FeBr6]3), CFSE is (3 x 2/5 o) - (2 x 3/5 o) = 0. The stabilization generated by the electrons in the lower orbitals is canceled out by the destabilizing effect of the electrons in the upper orbitals. d6- CFSE = 2.4o (LS) and if consider pairing energy (P), 2.4o- 3P. In HS case, CFSE = 0.4o and 0.4o-P. d7- 1.8o (LS)/1.8o3P & 0.8o(HS)/ 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.

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).

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

The pairing energy (P) and CFSE

Pairing energy (P) vs. DO 1. If DO < P, weak field; e.g., [Cr(H2O)6]2+ 2. If DO > P, strong field; e.g., [Cr(CN)6]4 3. If DO = P, ??; e.g., d4, d6 & d8. 3Distribution of d-electrons in t2g- and 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 (cm-1) spin state CFT predicted HS HS Observed expt. Relative magnitude of o and 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
o <P o >P o >P o <P o <P

d6

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

17600 17600 21000 21000 22500

10400 33000 32000 13000 93000

HS LS LS HS HS

HS LS LS HS HS

d7

Splitting in Tetrahedral geometry: 4-coordinate complexes, e.g., 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? 1. 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 (HScomplexes) t2g p eg q config. n Strong field (LScomplexes) t2g p eg q config. n

dx config.

d1 d2
d3 d4 d5 d6 d7 d8 d9 d10

t2g 0 eg 1 t2g 0 eg 2
t2g 1 eg 2 t2g 2 eg 2 t2g 3 eg 2 t2g 3 eg 3 t2g 3 eg 4 t2g 4 eg 4 t2g 5 eg 4 t2g 6 eg 4

1 2
3 4 5 4 3 2 1 0

t2g 0 eg 1 t2g 0 eg 2
t2g 0 eg 3 t2g 0 eg 4 t2g 1 eg 4 t2g 2 eg 4 t2g 3 eg 4 t2g 4 eg 4 t2g 5 eg 4 t2g 6 eg 4

1 2
1 0 1 2 3 2 1 0

DSP

Why sp = 1.3o?

Sq. planar
z out condition

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.

Applications of C.F. Theory

Ionic Radii:
1.0

Sc+2-unstable

Ionic radii

0.6 3d=0 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) 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

experimental values of CFSE 500 x x x x Calculated values of CFSE x x

1000

experimental values of CFSE x 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

700

Sc+2 Ti

+2

V+2 Cr

+2

Mn

+2

Fe

+2

Co

+2

Ni

+2

Cu

+2

Zn

+2

+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 high-spin 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 the absorbed Violet 4000 Blue 4350 Greenblue 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). Rarely, the energy of the photon absorbed corresponds exactly to the size of the gap ; Other factors (such as electron-electron repulsion and JahnTeller 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= 57kcal/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 5.9BM 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 a four-fold axis.

For example: (a) Elongation along z-axis (Z-out condition): two long bonds (zaxis) 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 No of d Distribution of es- in t2g and eg-orbitals 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) t2g6(sym)-eg2(sym) Predicted Distortion No distor. Slight D Slight D No distor. Strong D No distor. Slight D Slight D No distor. electrons d0 d1 d2 d3 d4 d5 d6 d7 d8

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) t2g6(sym)-eg2(unsym) Predicted Distortion No distor. Slight D Slight D No distor. Slight D Slight D No distor. Strong D Strong

Distor. leads
sq. planar 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 t2g-orbitals as

unsymmetrical 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 which point directly towards the ligands and are unsymmetrical i.e. contain 1, 3 and 2 electrons (only in LScomplexes), gave strong distortions, leading to tetragonal and even to sq. planar complexes.

Jahn-Teller Effect/ Theorem (1937): Explain, why certain complexes undergo distortion to assume distorted geometry? (i.e. Oh to 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 LS-

complexes (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 electrons in t2g- & eg-orbitals: 1. t2g3 dz21 dx2-y20 & 2. t2g3 dz20 dx2-y21 case 1, M+-L interaction along the z-axis is less than along the x- and y-axes, leads to a larger inter-ionic distance along the z-axis and hence a tetragonal structure (called z out condition or z-elongation). (ii) d9 ion (Cu2+ complex) e.g., aq. soln. of [Cu(NH3)4]2+. The tetragonal distortion

is so large that sq. planar complex results. 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.

Explanation of Distortion: Strong distortion mainly due to repulsion of ligands

by the electrons in eg-orbitals. In d4 ion (HS) and d9 ion (Cu+2 ion, LS & HS), case 1 showed the d-electron charge density becomes higher in z direction than x and

y direction. The dz2 orbital is half filled (d4) & completely filled and points at the
ligands on the z-axis offers greater shielding of the Cu+2 nucleus than the half filled dx2-y2 orbital, which points towards the ligands in the x, y-axes. The

ligands on the x- and y-axes experience a higher effective nuclear charge, while
those on z-axis experience a lower 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 dx2-y2 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 of the three 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 (being functions of the same variables x & y) 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 and not directly in the x, y and z directions along which the ligands are placed whereas 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.

Cu+2 (d9) ion: How the d orbital energy levels change in Cu+2 (d9) ion when the
regular Oh distorts? Let us consider the d-orbital energy levels change in the Cu+2 ion (d9 ion) when there occurs a small distortion of the type in which the

regular Oh becomes stretched along z-axis.

Here the splitting of the more stable Oh distortion corresponding to config. 1 has been considered, 1 and 2, which represent the splitting of the eg3 and t2g6-levels

respectively, both are much smaller than o and 2 is much smaller than 1.
o >>> 1> 2

The two eg-orbitals separate where dx2-y2 goes up as much as the other dz2 goes down; the t2g orbitals separate so that doubly degenerate pair (dyz and dxz) goes down only half as far as the single orbital dxy goes up. Hence, net energy change for t2g-electrons are zero, since four electrons (namely dz2) goes down, the t2g orbitals separate so that doubly degenerate pair (dyz and dxz) are stabilized by 4 x (-1/3 2) = - 4/3 2, while two electrons (dxy electrons) are destabilized by 2 x (+2/3 2) = +4/3 2. Thus in the splitting of t2g-levels: Net energy gain = energy gain + energy loss = + 4/3 2 + (-4/3 2) =0

The decrease in distortions energy due to J-T effect may be calculated as follows: 1. Elongation along Z axis (possibility): Energy of the complex corresponding to elongation, E1= 4 x (- 4 Dq - 2/3) + 2 x (- 4 Dq + 2 2/3) + 2 x (6 Dq - 1/2) + 1 x (6 Dq + 1/2) = - 6 Dq - 1/2

Energy of the complex without distortion is given by

E2 = 6 x (-4 Dq) + 3 x 6 Dq = - 6 Dq Decrease in energy due to J-T effect distortion is given by E2 E1 = - 6 Dq (- 6 Dq - 1/2) = 1/2. Thus increase in stability due to J-T distortion by 1/2.

2. Compression along Z axis (possibility): E3= 2 x (- 4 Dq 2 2/3) + 4 x (- 4 Dq +

2/3) + 2 x (6 Dq - 1/2) + 1 x (6 Dq + 1/2) = - 6 Dq - 1/2

Energy of the complex without distortion is given by E2 = 6 x (-4 Dq) + 3 x 6 Dq = - 6 Dq Decrease in energy due to J-T effect distortion is given by E2 E3 = - 6 Dq (- 6 Dq - 1/2) = 1/2. Thus increase in stability due to J-T distortion by 1/2. To sum up: 1. J-T distortions occur in Oh complexes in which metal ions have

the ground state config. t2g3 eg1, t2g4 eg1, t2g4 eg2, t2g5 eg2, t2g6 eg1 and
t2g6 eg3, t2g1, t2g2, t2g4 and t2g5. 2. J-T distortions are automatic not imposed phenomenon. 3. J-T effect is operative with anionic ligands and neutral too. 4. J-T effect shown by t2g orbitals is much weaker than that of eg orbitals.

Jahn-Teller effect on Electronic spectra of Complexes Electronic absorption bands in the spectra of coordination complexes are associated with d-d transitions (excitation of electrons from t2g to eg orbitals). Thus, the frequency of electromagnetic radiation absorbed should matches with the frequency of the two d orbitals involved in the electronic transition. For example, [Ti(H2O)6]3+- Oh complex, (d1 system). In ground state, electron occupies t2g orbitals and eg remains vacant. This complex absorbs in the visible region around = 5000 . The energy absorbed excites the solitary electron to one of the eg orbitals. The t2g1 eg1 electron transition should give rise to a single symmetrical absorption band in the spectrum of [Ti(H2O)6]+3. But is not so.

The observed absorption bond is unsymmetrical, which result of overlapping of

more than one absorption bands. This can be accounted for on the basis of J-T effect as follows:

% ABSORPTION

1000

1500

2000 (cm-1)

2500

3000

(Unsymmetrical absorption band observed in the spectrum of [Ti(H2O)6]+3). Suppose, the ground state electron is in dxy orbital (slightly stable complex). Reason: complex distorted to tetragonal geometry in which the Ti-OH2 bonds

along z axis are shorter than those along x and y axes (J-T effect). 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. Gap 2 can neither account for absorption of electromagnetic radiation

(visible region) nor can account for the 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, a considerable fraction of the complex ions at any moment present

containing the other possible tetragonally distorted geometry in which Ti-OH2 bonds along the z direction are elongated compared to other such bonds due to

the following reason:

The distorted geometry of Ti(H2O)6]+3 obtained by compression of Ti-OH2 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.

Factors determine the geometry of the complex ions: 1. J-T effect tends to favor the distorted geometry for Ti(H2O)6]+3 in which dxy is the lowest energy orbital. 2. The thermal energy available to the complex tends to equalize the population of the complex ions in the two distorted geometries. Due to this, an equilibrium condition between the populations of the complex ions in the two distorted geometries exists. This is known as dynamic J-T effect. Thus for dynamic J-T effect energy gap of t2g split up and eg split up 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 molecules in any distorted geometries. Hence, J-T effect will solely determine the stable

distorted geometry in which the complex will acquire. Thus, all the complexes will exist in only one stable distorted geometry is known as static J-T effect.

Here,[Ti(H2O)6]+3 exhibits dynamic J-T effect at rt (complex ions having both the
types of distorted geometries exist in equilibrium). The electron absorption spectra of [Ti(H2O)6]+3 will be an average of the electron absorption spectra of the two distorted geometries. Let us see what type of electron absorption spectra will be observed for the other distorted geometry in which Ti-OH2 bonds along z axis are longer than bonds along x and y directions. The ground state for such a geometry will be (dxz, dyz)1. The excited state dz21 will be of lower energy than the excited state dx2-y21. Thus, we can observed two transitions; t2g1 dx2-y21 and t2g1 dz21.

dx2-y2

dz 2
E

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.

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).

Discuss the electronic absorption spectrum of this geometry only. Unlike Ti+3 complexes, 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 of an electron from dz2 ---- dx2-y2 orbital by absorbing energy h1. (ii) Transition of an electron from dxy ---- dx2-y2 orbital by absorbing energy h2. (iii) Transition of an electron 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 J-T effect.

Limitations of CFT
(i) CFT considers only the metal ion d-orbitals and gives no consideration at all to other metal orbitals such as s-, p-orbitals and the ligand -orbitals. Therefore, 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 satisfactorily for the relative strengths of ligands, e.g. it gives no explanation as to why H2O appears in the spectrochemical series as a stronger ligand than OH-. (iii) According to CFT, the bond between the metal and ligands are purely ionic. It gives no account of the partly covalent nature of the metal-ligand bonds. Thus the effects directly dependent on covalently cannot be explained by CFT.

Ligand-Field Theory
The VBT and CFT explain some aspects of all of the properties of transitionmetal complexes. So, ligand-field theory developed based on MOT. The ligand-field model for an octahedral transition-metal complex such as [Co(NH3)6]3+ ion assumes that the 3d, 4s, and 4p orbitals on the metal overlap

with one orbital on each of the six ligands to form a total of 15 molecular
orbitals. Six-bonding molecular orbitals, whose energies are much lower than those of the original atomic orbitals. Six-antibonding molecular orbitals, whose energies are higher than those of the original atomic orbitals. Threenonbonding molecular orbitals, because they have essentially the same energy as the 3d atomic orbitals on the metal.

Ligand-field theory enables the 3d, 4s, and 4p orbitals on the metal to overlap

with orbitals on the ligand to form the octahedral covalent bond skeleton that
holds this complex together. At the same time, this model generates a set of five orbitals in the center of the diagram that are split into t2g and eg subshells,

as predicted by the crystal-field theory. As a result, we don't have to worry

about "inner-shell" versus "outer-shell" metal complexes. In effect, we can use the 3d orbitals in two different ways. We can use them to form the covalent

bond skeleton and then use them again to form the orbitals that hold the
electrons that were originally in the 3d orbitals of the transition metal.

An object is seen as black if it absorbs all colors of white light. A white object reflects all colors of white light equally.

If an object absorbs all colors but one, we see the color it does not absorb. The yellow strip in the following figure absorbs red, orange, green, blue, indigo and violet light. It reflects yellow light and we see it as yellow.

The yellow strip in the following figure looks yellow because it absorbs indigo light from white light. Indigo is the complementary color of yellow.

A solution containing the complex ion, [Cu(NH3)4]2+, is blue because the complex absorbs red and orange light, the complementary colors of blue and blue-green.

When the d-level is not completely filled, it is possible to promote and electron from a lower energy d-orbital to a higher energy d-orbital by absorption of a photon of electromagnetic radiation having an appropriate energy. Electromagnetic radiations in the visible region of the spectrum often possess the appropriate energy for such transitions.

Seeing Color The sensors in our eyes detect only those wavelengths in the visible portion of the electromagnetic spectrum.

Although visible light appears "white", it is made up of a series of colors. White light consists of three primary colors (red, yellow and blue). These primary colors can be mixed to make three secondary colors (orange, green and violet). Red + Yellow makes Orange Yellow + Blue makes Green Blue + Red makes Violet

Grass and leaves appear green because chlorophyll absorbs wavelengths in the red and blue portion of the visible spectrum. The wavelengths in between (green) are transmitted.

Transition Metal Complexes When light passes through a solution containing transition metal complexes, we see those wavelengths of light that are transmitted. The solutions of most octahedral Cu (II) complexes are blue. The visible spectrum for an aqueous solution of Cu (II), [Cu(H2O6]2+, shows that the absorption band spans the redorange-yellow portion of the spectrum and green, blue and violet are transmitted.

The absorption band corresponds to the energy required to excite an electron from the t2g level to the eg level.

Recall, the energy possessed by a light wave is inversely proportional to its wavelength. The Cu(II) solution transmits relatively high energy waves and absorbs the low energy wavelengths. This indicates that the band gap between the two levels is relatively small for this ion in aqueous solution.

d-Orbital Splitting The magnitude of the splitting of the d-orbitals in a transition metal complex depends on three things: 1. the geometry of the complex 2. the oxidation state of the metal 3. the nature of the ligands The Nature of the Ligands Some ligands only produce a small energy separation among the d-orbitals while others cause a wider band gap. Ligands that cause a small separation are called weak field ligands, and those that cause a large separation are called strong field ligands. The ordering of their splitting ability is called the spectrochemical series. A comparison of the visible absorption maxima for a number of cobalt (III) complexes shows the effects of ligands on the d-orbital band gap.

Magnetism
The magnetic properties of materials were recognized by the ancient Greeks, Romans, and Chinese, who were familiar with lodestone, an iron oxide mineral that attracts iron objects. Although the attractive or repulsive forces that act between magnetic materials are manifestations of magnetism familiar to everybody, the origin of magnetism lies in the atomic structure of matter. Despite the fact that magnetism can be explained only by the quantum theory developed at the beginning of the twentieth century, qualitative predictions of magnetic properties can be made within the context of classical physics. Magnetic forces originate in the motion of charged particles, such as electrons. The electrons "spin" around their axis and move in orbits around the nucleus of the atom to which they belong. Both motions generate tiny electric currents in closed loops that in turn create magnetic dipole fields, just as the current in a coil does. When placed in a magnetic field, the tiny magnetic dipole fields tend to align with the external field. According to their behavior in inhomogeneous magnetic fields, materials can be classified into three main categories: diamagnetic, paramagnetic, and ferromagnetic. Paramagnetic materials are attracted into a magnetic field. The main cause of this effect is the presence in the material of atoms that have a net magnetic moment composed of electron spin and orbital contributions.

Iron filings in a circular pattern around a magnet, indicative of the field of force of the magnet. When placed in a magnetic field, the magnetic moments of the atoms, which are otherwise randomly oriented, tend to align with the field and thus enhance the field. Paramagnetism is temperature dependent because increased thermal motion at higher temperatures impedes the alignment of the magnetic moments with the field. Diamagnetic materials are slightly repelled by a magnetic field. This effect occurs for materials that contain atoms in which the spin and orbital contributions to the magnetic moment cancel out. In this case, the interaction between the material and a magnetic field is caused by the occurrence of currents induced by the magnetic field in the atoms. The dipole fields corresponding to these currents are directed opposite to the applied magnetic field and cause expulsion of the material from the field.

Ferromagnetic materials contain atoms that have magnetic moments that are aligned even in the absence of an applied magnetic field because of mutual interactions, creating a sizable net magnetic moment for domains of the material. The magnetic moments of domains can be randomly oriented unless a magnetic field is applied to the material. Iron, cobalt, nickel, and their alloys are examples of ferromagnetic materials. These three elements are transition metals, and their atoms or ions have unpaired electrons in d orbitals. Rare-earth ions also have unpaired electrons situated in f orbitals. A detailed investigation of the properties of molecules that contain such metal ions in a magnetic field can provide significant information about how their electrons are distributed in orbitals. Typically, d orbitals of isolated atoms are degenerate (Figure 1a). This situation changes when the metal ions are part of molecules in which they experience a nonspherically symmetric environment. Figures 1b and 1c show the splitting of d orbitals for a transition metal ion that has six unpaired electrons and is situated in an environment of six atoms in an octahedral arrangement. Depending on the size of the splitting (the lighter shading in Figure 1) and the interelectron repulsion, the metal ion may have four unpaired electrons (Figure 1b) or no unpaired electrons (Figure 1c).

This difference in electron distribution leads to significant differences in the magnetic properties of the molecules that contain such ions, with the former being paramagnetic and the latter being diamagnetic. When there are multiple metal sites in a molecule, the spins at different metal ions can be either ferro-(parallel) or antiferro-magnetically (antiparallel) aligned to each other. Clever use of the magnetic properties for metal ions and of the interactions between spins manifested in molecular systems enables scientists to design and synthesize molecular systems with interesting properties, such as molecular magnets.

Magnetic materials are widely used for building technological devices and scientific tools. Classical examples are electromagnets that are used in motors, clutches, and breaking systems. The electromagnet makes use of an iron core situated in a solenoid through which electric current is passed. This current creates a magnetic field at the center of the solenoid that orients the magnetic moments in the domains of the iron core, which in turn results in a significant enhancement of the magnetic field at the core of the solenoid. Electromagnets can also be used to record information on magnetic tape, which has a ferromagnetic surface. Finally, although atomic nuclei have significantly smaller magnetic moments than electrons, the study of their interaction with magnetic fields has many important applications. They enable the scientists in the biological and medical fields to elucidate the structure of biologically relevant molecules such as proteins and to diagnose diseases using magnetic resonance imaging.

Magnetism in Transition Metal Complexes

Electronic Absorption Spectra of Metal Complexes explains in detail the origin of color in complexes of the transition metals. We learn that 6 sigma bonding ligands disposed about a metal ion at the vertices of a regular octahedron cause a splitting of the d orbitals of the metal into two sets, one triply degenerate set, n, of non-bonding orbitals (dxy,xz,yz), and one doubly degenerate set, s*, of antibonding orbitals (dz2,x2-y2). If these orbitals are partially filled with electrons originally belonging to the metal, and if the ligand field splitting, Do, between the two d orbital sets is such that visible light can cause the transition of an electron from the lower to the upper set, then the complex will be colored. We will now see that the very interesting and variable magnetic behavior of transition metals in complexes has its origin in the same basic structural features--split, partially filled d orbitals. With a couple of additional concepts, we can develop a satisfactory explanation of this magnetic behavior on the basis of the same theory that we used in discussing electronic spectra and color. We begin with an examination of the various types of magnetic behavior displayed by matter.

When a piece of matter is placed in a magnetic field, H (italic signifies a vector quantity), the matter becomes magnetically polarized; that is, a magnetic field is set up in the matter as a result of its presence within the external field, and it has been found experimentally that the strength of the internal field is proportional to the strength of the applied (external) field. We express this mathematically by equation (1) where M is the magnetic polarization of the matter and c is a (K-1): M = cH proportionality constant called the volume magnetic susceptibility. It has been further demonstrated by experiment that c may be either negative or positive. Materials for which c is small and less than 0 are called diamagnetic materials. Such behavior is always found for materials that contain no unpaired electrons. Most (but not all) organic compounds qualify as diamagnetic materials, since all their electrons are paired. Diamagnetic behavior is due to small fields induced in the sample by the applied field that are absent if no external field is present. All materials, regardless of any additional magnetic behavior they may display, exhibit diamagnetism. Materials for which c is greater than 0 are found to contain one or more unpaired electrons. If 0 < c <1 (the usual situation), the material is said to be paramagnetic. If on the other hand c > 1, the material is termed ferromagnetic.

Notice that c being greater than 1 means that the magnetic field set up in the sample of matter is greater in magnitude than the applied field! This behavior is exhibited by metallic iron (hence the word ferromagnetic), nickel, and some other metals. Ferromagnetism, however interesting, will not concern us any more at present. We are interested now in the phenomenon of paramagnetism, which arises whenever a molecule contains unpaired electrons. Oxygen is paramagnetic because it contains two unpaired electrons. NO2 is paramagnetic since it contains an odd number of electrons. (Any substance containing an odd number of electrons must be paramagnetic. Nature usually avoids this situation in compounds of the representative elements, but makes up for it in transition and inner transition elements, where there can be as many as 7 unpaired electrons per molecule.) Organic free radicals are paramagnetic due to the presence of an odd electron (remember the methyl radical, CH3, in free radical halogenation?). As it happens, complexes of most transition metals are paramagnetic as a result of the presence of unpaired electrons in the split d orbitals. We have already encountered an example of this in the complex Cr(NH3)63+, which contains 3 unpaired electrons, as discussed in the Appendix J.

Consider another example, this time involving FeIII, whose electronic configuration is [Ar]3d5 in the absence of ligands. We would expect the free gaseous ion to contain 5 unpaired electrons, as indeed it does--the electrons are distributed in the five degenerate d orbitals, according to the Pauli Exclusion Principle and Hund's Rules, as shown below:

Hund's Rules - electrons filling a set of degenerate orbitals will fill them so as to maintain their spins parallel for as long as possible. Similarly, the complex Fe(H2O)63+, present in strongly acid aqueous solution, contains 5 unpaired electrons. However, the very stable complex Fe(CN)63-, named hexacyanoferrate(-3), contains only one unpaired electron, even though it also contains Fe(III). We deduce from this that the nature of the ligands must in some way influence the pairing of electrons. But how? Let's call on what we have learned about the splitting of the d orbitals by the ligands. Figure 2 shows the situation in terms of an energy level diagram.

In the complex, 5 electrons must distribute themselves among the d orbitals,which as a result of the presence of 6 ligands are no longer all degenerate. There is no ambiguity about where the first three electrons will go--one electron will enter each of the three degenerate orbitals in the n set. The fourth electron, however, is faced with a choice: it can either pair up with one of the electrons in a lower orbital, requiring the expenditure of an amount of energy, P, called the pairing energy; or it can occupy one of the orbitals in the upper doubly degenerate set at the expense of the energy, Do , since the upper set, s*, is less stable by than the lower set, n. The electron will take the option which requires the expenditure of the least energy. If Do < P, it will occupy one of the s* orbitals. If Do > P, the electron will pair up in n. The fifth electron will be faced with the same choice, and will make the same decision. Two situations are therefore possible in octahedral complexes of FeIII:

In one case, five unpaired electrons are present. This is called the high spin (HS) case and must correspond to the situation in Fe(H2O)63+. In the second case, called the low spin (LS) case, only one unpaired electron is present--the maximum possible amount of electron pairing has occurred. This is the situation which in Fe(CN)63-. We conclude, then, that when H2O is the ligand, Do < P and that when CN- is the ligand, Do > P (P remains essentially the same for a given metal ion, regardless of ligand, and can be obtained from spectroscopic measurements of the free metal ion, in this case FeIII.) We call water a relatively "weak-field ligand" and cyanide a "strong-field ligand."

Any ion having as few as 4 or as many as 7 d electrons can exhibit either high- or low-spin behavior in an octahedral complex. You should work out the numbers of unpaired electrons expected in octahedral complexes of metal ions with configurations d1 to d9 to convince yourself of this. The theory that we have developed above explains beautifully most aspects of the magnetic behavior of transition metal complexes, the exceptions being the more subtle aspects that we will avoid for the time being. Let's turn now to the relationship between the number of unpaired electrons possessed by a molecule and its behavior in a magnetic field. There are two sources of magnetic behavior in matter: 1) orbital motion of electrons; 2) spin of electrons. We will deal with spin motion only now, since it is the most important source of magnetic behavior in complexes of transition metals. Pictured below is an electron spinning (rotating) about its own axis.

This motion is analogous to the rotation of the earth about its axis. Since the electron is a charged particle, this rotational motion constitutes an electric current. To see this more clearly, mentally replace the electron with a loop of wire in which a current is flowing:

Recall from your study of electricity and magnetism in physics, that a flow of current always generates a magnetic field. When the current is flowing in a loop, the direction of the magnetic field is perpendicular to the plane of the loop. Thus

The spin of the electron about its axis, since it is an electric current, similarly generates a magnetic field parallel to the axis of rotation. This magnetic field is called the spin magnetic moment of the electron, and is given the symbol mS. The arrow over the symbol indicates that the magnetic moment is a vector quantity. Now rotational motion of any kind always generates angular momentum, which is also a vector parallel to the axis of rotation. The magnetic moment and the angular momentum are therefore colinear vectors. Furthermore, their magnitudes are directly proportional. This is indicated in the following equation

(K-2): m = gL where L = angular momentum and g is the proportionality constant relating magnetic moment and angular momentum. When a paramagnetic sample is placed in an external magnetic field, the individual spin magnetic moments of the unpaired electrons all line up with the field, just as iron filings line up along the magnetic lines of flux generated by a bar magnet. Their vector sum is the magnetic polarization defined by equation (1). Thus we see that magnetic polarization, which is a macroscopic property, is related to individual spin magnetic moments, which are microscopic properties of the system. It can be shown that the magnetic moment of an individual ion in a sample is related to the number of unpaired electrons on the ion by the following equation. (K-3): mS = [n(n + 2)]1/2 Bohr magnetons The Bohr magneton is a convenient unit for expressing magnetic moments, and is defined in terms of fundamental constants as 1 BM = eh/4pmc. Here e = the charge on the electron, h = Planck's constant, m = the mass (K-4): mS = 2.84(cMT)1/2