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Transition Metal Chemistry and Coordination Compounds

Lecture 18-20

The Transition Metals

Oxidation States of the 1st Row Transition Metals


(most stable oxidation numbers are shown in red)

Ionization Energies for the 1st Row Transition Metals

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)

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+

Scandium

Titanium

Vanadium

Chromium

Manganese

Iron

Cobalt

Nickel

Copper

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 O N H H H H Cl

22.3

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

Coordination Compounds
bidentate ligand polydentate ligand (EDTA)

H2N

CH2

CH2

NH2

Bidentate and polydentate ligands are called chelating agents

EDTA Complex of Lead

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

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.
22.3

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

Transition Metal Chemistry and Coordination Compounds


Lecture 21-22

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.

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

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

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

Splitting of the d-Orbitals


Octahedral field Splitting Pattern:
The energy gap is referred to as (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.

Splitting of d orbitals in an octahedral field


eg
3/5 o

o
2/5 o

t2g

o is the crystal field splitting


E(t2g) = -0.4o x 3 = -1.2o E(eg) = +0.6o x 2 = +1.2o

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-

The magnitude of the splitting (metal ion effect)

Strong field

Weak field

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

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 LONGER

STRONGER FIELD LARGER SHORTER

Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

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 is small; High spin Lower orbital if is large: Low spin. Weak field ligands Small , High spin complex Strong field Ligands Large , Low spin complex

Placing electrons in d orbitals


Strong field
d1

Weak field

Strong field

Weak field d2

d3

d4

When the 4th electron is assigned it will either go into the higher energy eg orbital at an energy cost of 0 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 < o P > o Notes: the pairing energy, P, is made up of two parts. 1) Coulombic repulsion energy caused by having two electrons in same orbital

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

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.

To sum up
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.

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.

Bonding in Coordination Compounds

Splitting of d orbitals in a tetrahedral field


t2

t
e

t = 4/9o
Always weak field (high spin)

Bonding in Coordination Compounds

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

Octahedral, Tetrahedral & Square Planar


dx2-y2 dz2
Octahedral Tetrahedral
M
M

CF Splitting pattern for various molecular geometry

dx2-y2 dxy

dxy dyz dxz

Square planar
M

dz2 dxy dyz dxz dx2-y2 dz2


Small High Spin

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

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

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

Colour in Coordination Compounds

E = hn

22.5

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) = hn= = = 4.23 x 10-19 J 470 x 10-9 m
(kJ/mol) = 4.23 x 10-19 J/atom x 6.022 x 1023 atoms/mol = 255 kJ/mol
22.5

Color Absorption of Complexes


Complex Ion

3+ Co

of Color of Light Color of Complex The Wavelength Colors of Some Complexes light absorbed Absorbed 3+ 3+ the 700 Co [CoF6]of (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.

Colors & How We Perceive it

650

580

800

560

Artist color wheel showing the colors which are complementary to one another and the wavelength range of each color.

400

430

490

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+

Black and White


When a sample absorbs light, what we see is the sum of the remaining colors that strikes our eyes.

If a sample absorbs all wavelength of visible light, none reaches our eyes from that sample. Consequently, it appears black.

If the sample absorbs no visible light, it is white or colorless.

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

Light absorption Properties of Metal Complexes


Recording the absorption Spectrum

Chemistry In Action: Coordination Compounds in Living Systems Hemoglobin

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

Porphyrin ring delocalized e-

Phytol tail

Chemistry In Action: Cisplatin The Anticancer Drug

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