Transition Metal Chemistry and Coordination Compounds

Lecture 18-20
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The Transition Metals

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Oxidation States of the 1st Row Transition Metals

(most stable oxidation numbers are shown in red)

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Ionization Energies for the 1st Row Transition Metals

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Aqueous oxoanions of transition elements

One of the most characteristic chemical properties of these elements is the occurrence of multiple oxidation states. Mn(II) Mn(VI) Mn(VII)

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

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

[V(H2O)6]2+

[V(H2O)6]3+

[Cr(NH3)6]3+

[Cr(NH3)5Cl ]2+

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Scandium

Titanium

Vanadium

Chromium

Manganese

Iron

Cobalt

Nickel

Copper

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Chemistry of Iron and Copper

Iron ore- Magnetite Fe3O4 6.2% in earths crust after Al Haematite-Fe2O3 Siderite-FeCO3 Prepration in Blast Furnace Iron react with HCl to give H2 Conc. Sulfuric and nitric acid renders the metal passive by forming a thin layer of Fe3 O4 some imp. Compounds: in +2 and +3 FeO (black), FeSO4.7H2O (green), FeCl2 (Yellow), FeS (Black) etc.

Copper ore- Chalcopyrite CuFeS2 Rare element 6.8 x 10-3 % Obtained by roasting and can be purified by electrolysis. After silver, Cu has the highest electrical conductivity and is a good thermal conductor. Used in alloys, cables, plumbing and coins. It reacts only with hot conc. Sulfuric and nitric acids. +1 and +2 componds in which +1 are diamagmetic. CuO (Black), CuSO4.5H2O (blue) and CuS (black)
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Coordination Compounds
A coordination compound typically consists of a complex ion and a counter ion.

A complex ion contains a central metal cation bonded to one or more molecules or ions.
The molecules or ions that surround the metal in a complex ion are called ligands. A ligand has at least one unshared pair of valence electrons C O
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N H H H H

Cl

Coordination Compounds
The atom in a ligand that is bound directly to the metal atom is the donor atom. N O H H H H H

The number of donor atoms surrounding the central metal atom in a complex ion is the coordination number. Ligands with: one donor atom two donor atoms three or more donor atoms monodentate bidentate polydentate H2O, NH3, Clethylenediamine EDTA

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Coordination Compounds
bidentate ligand polydentate ligand (EDTA)

H2N

CH2

CH2

NH2

Bidentate and polydentate ligands are called chelating agents

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EDTA Complex of Lead

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What are the oxidation numbers of the metals in K[Au(OH)4] and [Cr(NH3)6](NO3)3 ? OH- has charge of -1 K+ has charge of +1 ? Au + 1 + 4x(-1) = 0
Au = +3 NO3- has charge of -1

NH3 has no charge ? Cr + 6x(0) + 3x(-1) = 0

Cr = +3

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Naming Coordination Compounds

The cation is named before the anion. Within a complex ion, the ligands are named first in alphabetical order and the metal atom is named last.

The names of anionic ligands end with the letter o. Neutral ligands are usually called by the name of the molecule. The exceptions are H2O (aqua), CO (carbonyl), and NH3 (ammine).
When several ligands of a particular kind are present, the Greek prefixes di-, tri-, tetra-, penta-, and hexa- are used to indicate the number. If the ligand contains a Greek prefix, use the prefixes bis, tris, and tetrakis to indicate the number. The oxidation number of the metal is written in Roman numerals following the name of the metal. If the complex is an anion, its name ends in ate.
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What is the systematic name of [Cr(H2O)4Cl2]Cl ? tetraaquodichlorochromium(III) chloride

Write the formula of tris(ethylenediamine)cobalt(II) sulfate [Co(en)3]SO4

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What is the systematic name of Na[AuF4] ?

Sodium tetrafluoroaurate(III)

What is the systematic name of K3[Fe(CN)6] ?

Potassium hexacyanoferrate(III)

What is the systematic name of [Cr(en)3]Cl 3?

tris(ethylenediamine)chromium(III) chloride

What is the systematic name of [Ni(CO)4] ?

Tetracarbonylnickel(0)
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Transition Metal Chemistry and Coordination Compounds

Lecture 21-22

Mr. Harminder Singh

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Structure of Coordination Compounds

Coordination number

Structure

2
4 6

Linear
Tetrahedral or Square planar Octahedral

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Structure of Coordination Compounds

Stereoisomers are compounds that are made up of the same types and numbers of atoms bonded together in the same sequence but with different spatial arrangements. a. Geometric isomers b. Optical isomers

Geometric isomers are stereoisomers that cannot be interconverted without breaking a chemical bond. They usually come in pairs (cis & trans). They have quite different colors, melting points, dipole moments and chemical reactivities.

cis-[Pt(NH3)2Cl2]

trans-[Pt(NH3)2Cl2]
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Structure of Coordination Compounds

trans

cis

cis-[Co(NH3)4Cl2]

trans-[Co(NH3)4Cl2]

Are these additional geometric isomers of [Co(NH3)4Cl2]?

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Structure of Coordination Compounds

Optical isomers are nonsuperimposable mirror images.

cis-[Co(en)2Cl2] optical isomers chiral

trans-[Co(en)2Cl2] not optical isomers achiral

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Structure of Coordination Compounds

Chiral molecules are optically active. Dextrorotatory (d) & levorotory (l) (collectivelly enantiomers: equimolar mixture is called racemic mixture , the net rotation is zero. Achiral molecules are optically in active

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Bonding in Coordination compounds:

Old theories: Werner and Sidgwick

New theories: VBT, CFT, LFT, MOT

CRYSTAL FIELD THEORY

Accounts for color and magnetic properties

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Crystal field splitting in Octahedral complexes

All equal in energy in the absence of ligands!

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Crystal-Field Theory
Model explaining bonding for transition metal complexes
Originally developed to explain properties for crystalline material Basic idea: Electrostatic interaction between lone-pair electrons
result in coordination.

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Energetics
CFT - Electrostatic between metal ion and donor atom
i) Separate metal and ligand high energy ii) Coordinated Metal - ligand stabilized iii) Destabilization due to ligand -d electron repulsion iv) Splitting due to octahedral field.

ii
iv iii

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Bonding in Coordination Compounds

Isolated transition metal atom Bonded transition metal atom Crystal field splitting ( D) is the energy difference between two sets of d orbitals in a metal atom when ligands are present. The magnitude of D depends on the metal and the nature of the ligands; it has a direct effect on the color and magnetic properties of complex ions.
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d-Orbitals and Ligand Interaction (Octahedral Field)

Ligand s approac h metal

d-orbitals pointing directly at axis are affected most by electrostatic interaction

d-orbitals not pointing directly at axis are least affected (stabilized) by electrostatic interaction
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Ligand-Metal Interaction
Crystal Field Theory - Describes bonding in Metal Complexes
Basic Assumption in CFT: Electrostatic interaction between ligand and metal

d-orbitals align along the octahedral axis will be affected the most. More directly the ligand attacks the metal orbital, the higher the the energy of the d-orbital. In an octahedral field the degeneracy of the five d-orbitals is lifted
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Splitting of the d-Orbitals

Octahedral field Splitting Pattern:
The energy gap is referred to as D (10 Dq) , the crystal field splitting energy.

The dz2 and dx2y2 orbitals lie on the same axes as negative charges.
Therefore, there is a large, unfavorable interaction between ligand (-) orbitals. These orbitals form the degenerate high energy pair of energy levels. The dxy , dyx and dxz orbitals bisect the negative charges. Therefore, there is a smaller repulsion between ligand & metal for these orbitals.

These orbitals form the degenerate low energy set of energy levels.

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Color of a Substance

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Absorption and Reflection

If the sample absorbs all but orange, the sample appears orange.

Further, we also perceive orange color when visible light of all colors except blue strikes our eyes. In a complementary fashion, if the sample absorbed only orange, it would appear blue; blue and orange are said to be complementary colors.

650
750 400

580

560

430

490
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Light absorption Properties of Metal Complexes

Recording the absorption Spectrum

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Colour in Coordination Compounds

DE = hn

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The absorption maximum for the complex ion [Co(NH3)6]3+ occurs at 470 nm. What is the color of the complex and what is the crystal field splitting in kJ/mol?

Absorbs blue, will appear orange.

hc (6.63 x 10-34 J s) x (3.00 x 108 m s-1) D = hn = = = 4.23 x 10-19 J l 470 x 10-9 m

D (kJ/mol) = 4.23 x 10-19 J/atom x 6.022 x 1023 atoms/mol = 255 kJ/mol
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Complex Influence on Color

Compounds of Transition metal complexes solution.

650 800 400 430

580 560 490

[Fe(H2O)6

]3+

[Ni(H2O)6]2+

[Co(H2O)6]2+

[Zn(H2O)6]2+ [Cu(H2O)6]2+
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Color Absorption of Complexes

Complex Ion

3+ Co

The Wavelength of Some Complexes Colors of Color of Light Color of Complex light absorbed Absorbed 3+ Co3+ [CoF6]of the 700 (nm) Ion Red Green
600, 420 600, 400 475, 340 470, 340 310 Yellow, violet Yellow, violet Blue, violet Blue, ultraviolet Ultraviolet Dark green Blue-green Yellow-orange Yellow-orange Pale Yellow

[Co(C2O4)3] 3+ [Co(H2O)6] 3+ [Co(NH3)6] 3+ [Co(en)3] 3+ [Co(CN)6] 3+

The complex with fluoride ion, [CoF6]3+ , is high spin and has one absorption band. The other complexes are low spin and have two absorption bands. In all but one case, one of these absorptionsis in the visible region of the spectrum. The wavelengths refer to the center of that absorption band.
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The spectrochemical series

For a given ligand, the color depends on the oxidation state of the metal ion. For a given metal ion, the color depends on the ligand.

I- < Cl- < F- < OH- < H2O < SCN- < NH3 < en < NO2- < CN- < CO

WEAKER FIELD
SMALLER D LONGER l

STRONGER FIELD LARGER D SHORTER l

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Splitting of d orbitals in an octahedral field

eg
3/5 Do

Do
2/5 Do

t2g

Do is the crystal field splitting

E(t2g) = -0.4Do x 3 = -1.2Do E(eg) = +0.6Do x 2 = +1.2Do
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The magnitude of the splitting (ligand effect)

Strong field

Weak field

The spectrochemical series CO, CN- > phen > NO2- > en > NH3 > NCS- > H2O > F- > RCO2- > OH- > Cl- > Br- > I-

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The magnitude of the splitting (metal ion effect)

Strong field

Weak field

D increases with increasing formal charge on the metal ion D increases on going down the periodic table

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Electron Configuration in Octahedral Field

Electron configuration of metal ion: s-electrons are lost first. Ti3+ is a d1, V3+ is d2 , and Cr3+ is d3 Hund's rule: First three electrons are in separate d orbitals with their spins parallel. Fourth e- has choice: Higher orbital if D is small; High spin Lower orbital if D is large: Low spin. Weak field ligands Small D , High spin complex Strong field Ligands Large D , Low spin complex

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Placing electrons in d orbitals

Strong field
d1

Weak field

Strong field

Weak field d2

d3

d4

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When the 4th electron is assigned it will either go into the higher energy eg orbital at an energy cost of D0 or be paired at an energy cost of P, the pairing energy. d4 Strong field = Low spin (2 unpaired) Weak field = High spin (4 unpaired)

P < Do

P > Do

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Pairing Energy, P
The pairing energy, P, is made up of two parts. 1) Coulombic repulsion energy caused by having two electrons in same orbital. Destabilizing energy contribution of Pc for each doubly occupied orbital.

2) Exchange stabilizing energy for each pair of electrons having the same spin and same energy. Stabilizing contribution of Pe for each pair having same spin and same energy
P = sum of all Pc and Pe interactions
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Placing electrons in d orbitals d5 d6 d7

1 u.e.

5 u.e.

0 u.e.

4 u.e.

1 u.e.

3 u.e.

d8

d9

d10

2 u.e.

2 u.e.

1 u.e.

1 u.e.

0 u.e.

0 u.e.
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Electron Configuration for Octahedral complexes of metal ion having d1 to d10 configuration [M(H2O)6]+n.
Only the d4 through d7 cases have both high-spin and low spin configuration.

To sum up

Electron configurations for octahedral complexes of metal ions having from d1 to d10 configurations. Only the d4 through d7 cases have both high-spin and low-spin configurations.
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Bonding in Coordination Compounds

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Splitting of d orbitals in a tetrahedral field

t2

Dt
e

Dt = 4/9Do
Always weak field (high spin)
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Bonding in Coordination Compounds

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A crystal-field aproach: from octahedral to tetrahedral

L L M L L L L L M L L L

Less repulsions along the axes where ligands are missing

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Octahedral, Tetrahedral & Square Planar

dx2-y2 dz2
Octahedral Tetrahedral
M
M

CF Splitting pattern for various molecular geometry

dx2-y2 dxy dyz dxz

Square planar
M

dxy

dz2 dxy dyz dxz

Pairing energy Vs. D Weak field D < Pe Strong field D > Pe

dx2-y2 dz2
Small D High Spin

dxzdyz
Mostly d8 (Majority Low spin) Strong field ligands i.e., Pd2+, Pt2+, Ir+, Au3+
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Applications of coordination compounds

Colour of transition metal complexes Number of unpaired electrons and magnetic properties Coordination compounds in living systems Coordination compounds in medicine

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Chemistry In Action: Coordination Compounds in Living Systems Hemoglobin

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Chlorophyll a & b
Chl a has a methyl group Chl b has a carbonyl group

Porphyrin ring delocalized e-

Phytol tail
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Chemistry In Action: Cisplatin The Anticancer Drug

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