Chemistry: A Molecular Approach, 1st Ed.

Nivaldo Tro

Chapter 24 Transition Metals and Coordination Compounds

Roy Kennedy Massachusetts Bay Community College Wellesley Hills, MA
2007, Prentice Hall

Coordination Chemistry Gemstones

The colors of rubies and emeralds are both
due to the presence of Cr3+ ions the difference lies in the crystal hosting the ion
Some Al3+ ions in Al2O3 are replaced by Cr3+
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Some Al3+ ions in Be3Al2(SiO3)6 are replaced by Cr3+

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Complex Ion Color

The observed color is the complimentary color of the one that is absorbed

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i-Clicker 24-1:

Technetium is a rare element found on earth with isotopes that can be used in medical testing. Which of the following is the correct ground state electron configuration of Tc4+?

A. Tc4+: [Kr]5s24d1 B. Tc4+: [Kr]5s04d3 C. Tc4+: [Kr]5s14d2

D. Tc4+: [Ar]4s03d3 E. Tc4+: [Kr]5s24d5

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Properties and Electron Configuration of Transition Metals

The properties of the transition metals are similar to
each other
and very different to the properties of the main group metals high melting points, high densities, moderate to very hard, and very good electrical conductors

In general, the transition metals have two valence

electrons we are filling the d orbitals in the shell below the valence
Group 1B and some others have 1 valence electron due to promotion of an electron into the d sublevel to fill it form ions by losing the ns electrons first, then the (n 1)d

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Coordination Compounds
When a complex ion combines with counter-ions to
make a neutral compound it is called a coordination compound The primary valence is the oxidation number of the metal The secondary valence is the number of ligands bonded to the metal
coordination number

Coordination number range from 2 to 12, with the most

common being 6 and 4 CoCl36H2O = [Co(H2O)6]Cl3
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Coordination Compounds
3+ Ligands

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What is the charge on the central ion?

Complex Ion Formation

Complex ion formation is a type of Lewis acidbase reaction A bond that forms when the pair of electrons is donated by one atom is called a coordinate covalent bond

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Ligands with Extra Teeth

Some ligands can form more than one
coordinate covalent bond with the metal atom
Lone pairs on different atoms that are separate enough so that both can reach the metal

Chelate is a complex ion containing a

multidentate ligand
Ligand is called the chelating agent

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EDTA a Polydentate Ligand

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Complex Ions with Polydentate Ligands

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Geometries in Complex Ions

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Naming Coordination Compounds

1) Determine the name of the noncomplex ion 2) Determine the ligand names and list them in 3) 4)
alphabetical order Determine the name of the metal cation Name the complex ion by:
1) Name each ligand alphabetically, adding a prefix in front of each ligand to indicate the number found in the complex ion 2) Follow with the name of the metal cation

5) Write the name of the cation followed by the name of

the anion
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Common Ligands

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Common Metals found in Anionic Complex Ions

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i-Clicker 24-2:

What is the correct name of the coordination compound [Pt(NH3)5Cl]Br3?

A. pentaamminechloroplatinum(IV) tribromide B. triamminechloroplatinum(IV) bromide C. pentaamminebromoplatinum(IV) chloride D. pentaamminechloroplatinum(IV) bromide E. Chloropentaammineplatinum(IV) bromide

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i-Clicker 24-3:

What is the correct formula for sodium tetrachloronickelate(II)

A. Na2[NiCl4] B. Na2[Ni4Cl4] C. Na2[NiCl4]2+ D. Na2[NiCl3] E. Na[Ni4Cl]2+

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Isomers
Structural isomers are molecules that have the
same number and type of atoms, but they are attached in a different order Stereoisomers are molecules that have the same number and type of atoms, and that are attached in the same order, but the atoms or groups of atoms point in a different spatial direction
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Linkage Isomers

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Geometric Isomers
geometric isomers are stereoisomers that differ
in the spatial orientation of ligands
cis-trans fac-mer isomerism cis-trans isomerism isomerismin in inoctahedral octahedral square-planar complexes complexes complexes MA MA3 MA B3 4B 2 2B2

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Ex. 24.5 Draw the structures and label the type for all isomers of [Co(en)2Cl2]+
the ethylenediamine ligand (en = H2NCH2CH2NH2) is bidentate each Cl ligand is monodentate octahedral MA4B2

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[Co(en)3]3+

Optical Isomers
optical isomers are
stereoisomers that are nonsuperimposable mirror images of each other

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Ex 24.7 Determine if the cis-trans isomers of [Co(en)2Cl2]+ are optically active

draw the mirror

image of the given isomer and check to see if they are superimposable
trans isomer identical to its mirror image cis isomer mirror image is nonsuperimposable nooptical opticalisomers isomerism
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Bonding in Coordination Compounds Electrostatic Model Overly Simplistic but USEFUL! Works well for Main Group metal complexes. Assumes a purely ionic attraction between the
central metal ion and charged or partially charged polar ligands. It predicts ligand-metal bonds will increase in strength with increasing charge density on the central metal atom. Al(H2O)63+ > Mg(H2O)62+
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Bonding in Coordination Compounds Electrostatic Model

It predicts ligand-metal bonds will increase in
strength with increasing ligand polarity. Al(H2O)63+ > Al(NH3)63+ It Fails to adequately explain 1) Color; 2) Stability; 3)Paramagnatism; 4) Square planar geometries, in transition metal complexes.

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i-Clicker 24-4:
Which forms the strongest ligand-metal ion bond?

A. Al(H2O)63+ B. Al(NH3)63+ C. Mg(H2O)62+

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Bonding in Coordination Compounds Valence Bond Theory

Bonding take place when the filled atomic
orbital on the ligand overlaps an empty atomic orbital on the metal ion Explain geometries well, but doesnt explain color or magnetic properties

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Valence Bond Theory

A covalent bond forms when the orbital of one atom overlaps with the orbital of another atom In transition metal complexes, covalent bonds are formed through the overlap of a filled ligand orbital with an empty transition metal orbital

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Valence Bond Theory

Hybridization determines the geometry of the complex
If the geometry is know the hybrid orbitals used in bonding are known

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Valence Bond Theory

Geometry 2 4 Coord # Linear Tetrahedral Hybrid Orbitals sp sp3

4 6

Square Planar Octahedral

dsp2 d2sp3, sp3d2

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Bonding in Coordination Compounds Crystal Field Theory (CFT)

More sophisticated model than the electrostatic model. More accurate than the Valence Bond Theory. Still simple enough for general utility. Assumes that ligands retain their electrons and central ions retain their electrons. Assumes that the d-electrons in the metal atoms are influenced (repelled) by the electron pairs in the ligands.

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Bonding in Coordination Compounds Crystal Field Theory (CFT)

Bonds form due to the attraction of the electrons on the

ligand for the charge on the metal cation Electrons on the ligands repel electrons in the unhybridized d orbitals of the metal ion The result is the energies of orbitals the d sublevel are split The difference in energy depends the complex and kinds of ligands
Crystal field splitting energy Strong field splitting and weak field splitting
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Splitting of d-Orbital Energies due to Ligands in a Octahedral Complex

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Complex Ion Color and Crystal Field Strength

The colors of complex ions are due to electronic
transitions between the split d-sublevel orbitals The wavelength of maximum absorbance can be used to determine the size of the energy gap between the split d-sublevel orbitals Ephoton = hn = h(c/l) = D
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Ligand and Crystal Field Strength

The strength of the crystal field depends in large
part on the ligands
Strong field ligands include: CN > NO2 > en > NH3 Weak field ligands include H2O > OH > F > Cl > Br > I

Crystal field strength increases as the charge on

the metal cation increases
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Magnetic Properties and Crystal Field Strength

The electron configuration of the metal ion with split d

orbitals depends on the strength of the crystal field The 4th and 5th electrons will go into the higher energy dx2-y2 and dz2 if the field is weak and the energy gap is small leading to unpaired electrons and a paramagnetic complex The 4th thru 6th electrons will pair the electrons in the dxy, dyz and dxz if the field is strong and the energy gap is large leading to paired electrons and a diamagnetic complex
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Strong and Weak Field Splitting

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Low Spin & High Spin Complexes

diamagnetic

paramagnetic
high-spin complex

low-spin complex

Only electron configurations d4, d5, d6, or d7 can have low or high spin
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 because the ligand approach interacts more

strongly with the planar orbitals in the tetrahedral geometry, their energies are raised most high-spin complexes

Tetrahedral Geometry and Crystal Field Splitting

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 d8 metals the most complex splitting pattern most are low-spin complexes

Square Planar Geometry and Crystal Field Splitting

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Crystal Field Theory

Crystal field theory helps to explain the colors of transition metal complexes Why are transition metal complexes colored?
They absorb specific wavelengths of light in the visible portion of the electromagnetic spectrum The wavelengths NOT absorbed are transmitted and seen as colour The colour observed in complimentary to the colour absorbed

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Complex Ion Color

The observed color is the complimentary color
of the one that is absorbed

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The Visible Spectrum

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The Visible Spectrum

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Colours of Transition Metals

What happens when visible light is absorbed by an atom, ion or molecule? The energy of light is used to raise the electron(s) to a higher energy level from a lower energy level
From a lower energy orbital to a higher energy orbital

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Colours of Transition Metals

The light energy absorbed corresponds to the energy difference between the two orbitals Because the energy levels are quantized, light is absorbed only if its energy exactly matched the energy difference between the two orbitals

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Electron Jumping
For transition metal complexes , the splitting between the d orbital energies in the crystal field corresponds to the energies of visible light Absorption of light raises an electron from a lower energy d orbital to a higher energy d orbital in the crystal field

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Crystal Field Theory

__ __
White Red Light Absorbed

__ __
Green-Blue Observed

Light

__ __ __

__ __ __

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Colour of Transition Metals

Transition metal complexes absorb energies of visible light corresponding to the crystal field splitting energies
There we see colour

The absorbed energy is used to promote and electron from a lower energy orbital to a higher energy one

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Colour of Transition Metal Complexes

Compounds that have no d electrons or have 10 d electrons can not absorb visible light because no electrons can be moved from lower energy orbitals to higher energy ones
These complexes are colourless!

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Titanium Dioxide
TiO2 is the white pigment used in paper and paint Why is it white? Ti4+ has no d-electrons

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More Peculiarities
Different complexes can exhibit different colours even when the central transition metal is in the same oxidation state How does this happen?

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Colour of Transition Metal Complexes

The colour of a transition metal complex depends on the magnitude of
The magnitude of depends on the nature of the ligand(s) bonded to the metal The larger , the higher the energy of absorbed light The smaller , the lower the energy of absorbed light

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Colour of Transition Metal Complexes

Some ligands induce a larger splitting of the d orbitals than others
Thus the colour of transition metals depends on the nature of the ligands

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Spectrochemical Series

Ligands can be arranged according to their ability to split the d orbitals

That is according to

This is referred to as the spectrochemical series

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Electronic Configurations of Transition Metal Complexes

Electrons tend to fill orbitals according to the following tendencies
Electrons spread out to minimize electronic repulsions Electrons tend to occupy the lowest energy levels first

These tendencies are NOT always followed by transition metal complexes

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Electronic Configuration of Transition Metal Complexes

For transition metal complexes, the order that electrons fill orbitals depends upon both and the electron pairing energy If > P, is large strong ligand field electrons pair up in the lower energy orbitals If < P is small, weak ligand field electrons spread out across the d orbitals before they pair up
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Orbital Diagrams
For octahedral d1 d3 all complexes are high spin all electrons in the lower energy d subshells

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Orbital Diagrams
The situation is more complex for d4 d7 complexes

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Spectrochemical Series

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Spectrochemical Series

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Electronic Configurations of Transition Metals

How to figure out electronic configurations of octahedral transition metal complexes
Determine the oxidation number of the metal Determine the number of d electrons Determine whether the ligand field is strong or weak
Weak field high spin Strong field low spin

Draw the energy level diagram

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Orbital Levels in Tetrahedral Complexes

Could you predict the higher and lower energy d orbitals?
Remember the splitting is due to the repulsive forces between electrons Which orbitals are directed along the tetrahedral axis? These will be higher energy

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Square Planar Complexes

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Crystal Field Stabilization Energy

A measure of the stabilization of the complex

Free Metal Ion

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Problem
1. Calculate the CFSE for both high spin and low spin octahedral complexes of Co(gly)63-. Which is preferred? = 21, 476 cm-1, P = 23,625 cm-1,

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Problem 2
What is t if the compound absorbs at 690 nm? Solution: = 690 nm (1m/109 nm) = 6.90 x 107 m
= hc/ = (6.626 x 1034 Js)(2.998 x 108 m/s) 6.90 x 107 m = 2.88 X 10-19 J
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Applications of Coordination Compounds

extraction of metals from ores use of chelating agents in heavy metal poisoning
EDTA for Pb poisoning silver and gold as cyanide complexes nickel as Ni(CO)4(g)

chemical analysis
qualitative analysis for metal ions
blue = CoSCN+ red = FeSCN2+
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Applications of Coordination Compounds

commercial coloring agents
prussian blue = mixture of hexacyanoFe(II) and Fe(III)
inks, blueprinting, cosmetics, paints

biomolecules
porphyrin ring cytochrome C hemoglobin chlorphyll
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chlorophyll

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Applications of Coordination Compounds

carbonic anhydrase
catalyzes the reaction between water and CO2 contains tetrahedrally complexed Zn2+

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Applications of Coordination Compounds

Drugs and Therapeutic Agents
cisplatin
anticancer drug

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