7/24/2012

Chapter 19: Transition Metals

and Coordination Chemistry
19.1 Survey of transition metals
19.2 1st-row transition metals
19.3 Coordination compounds
19.4 Isomerism
19.5 Bonding in complex ions: The localized electron model
19.6 The crystal field model
19.7 The molecular orbital model
19.8 The biological importance of coordination complexes

Chapter 19: Transition Metals

and Coordination Chemistry
Filling d-orbital shells
3d
4d
5d

Figure 19.1

Filling f-orbital shells

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General Properties of Transition Metals

Metallic luster
High electrical and thermal conductivity (Ag, Cu)
Wide range of melting points (e.g. W @ 3400C,
Hg @ -39C) and hardness
Wide range of reactivity toward O2
Fe3O4 - magnetite (magnetic recording material)
Fe2O3 rust (scales off complete corrosion)
Oxides of Cr, Co, and Ni- very hard, protective
Coinage metals (Au, Ag, Pt, Pd) do not react
readily with O2 (noble metals)

More General Properties of Transition Metals

Easily oxidized
Readily form ionic complexes
e.g. Fe(H2O)62+, [Co(NH3)4Cl2]+

Many coordination compounds are colored

Many coordination compounds are paramagnetic

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Some important aspects of transition metal ions:

1. The valence electrons are in d orbitals
2. The d orbitals do not have a large radial extension
3. The d orbitals are, therefore, mostly nonbonding in
complexes of transition metal ions
For these reasons, the effects of redox changes are
substantially smaller for transition metals than for
main group elements
Review Section 12.13!

Electron configurations of the neutral

transition metal elements

Figure 12.27

3d start to fill after 4s is full

Cr and Cu are exceptions to trend: both are 4s1 3dn
Neutral TM: 3d and 4s orbitals similar in energy
3d orbitals for TM ions much less E than 4s, so 4s electrons
leave first (1st row TM ions do not have 4s electrons)

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Orbital Occupancy of Period 4 Transition Metals

3d

4p

Unpaired
Electrons

Element

4s

Sc

Ti

Cr

Mn

Fe

Co

Ni

Cu

Zn

1
2
3

When you oxidize a transition metal, remove s electrons first!

Oxidation States
See Table 19.2 for common oxidation states of the
1st-row transition metals

+1 up to +7 are observed, with +2 and +3 most

common
Highest O.S. is loss of all 4s and 3d electrons
As the oxidation state is increased, the d orbitals are
stabilized, and the metals get harder to oxidize
further

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Standard Reduction Potentials

Consider the reduction half-reaction:
Mn+ + neM
Reduction potentials (E) for 1st-row transition metals in
aqueous solutions:

Sc
Ti
V
Mn
Cr
Zn
Fe
Co
Ni
Cu

-2.08 V
-1.63 V
-1.2 V
-1.18 V
-0.91 V
-0.76 V
-0.44 V
-0.28 V
-0.23 V
0.34 V

reducing ability

Sc3+ + 3eTi2+ + 2eV2+ + 2eMn2+ + 2eCr2+ + 2eZn2+ + 2eFe2+ + 2eCo2+ + 2eNi2+ + 2eCu2+ + 2e-

See Table 19.3 (opposite signs b/c reduction vs. oxidation potentials)

Oxidation Potentials

(opp. sign from standard reduction potentials)

Consider the oxidation
half-reaction:
M

Mn+ + ne-

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Transition-metal complexes
are extremely colorful.
Color is influenced by:
metal ion (dn configuration),
oxidation state, and
coordinated ligands.

K3[Fe(CN)6]

[Co(NH3)5Cl]Cl2

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Oxidation States of Mn
2 MnO4-(aq) + 5 H2C2O4(aq) + 6 H+(aq)
2 Mn2+(aq) + 10 CO2(g) + 8 H2O(l)

* Observe several intermediates (mixtures of MnO4-, lower O.S. of

Mn, and Mn(III)-oxalate complexes)
Table 19.6

Oxidation State influences color

+2

V2+(aq)

+3

V3+(aq)

+4

VO2+(aq)
+5

VO2+(aq)

V0(s)

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Oxidation States of Vanadium

Different colors are due to different numbers of
electrons in the highest-occupied MOs of each Vcontaining polyatomic ion.
V +4 is the most common oxidation state. V +5 is
easily converted to V+4 by the mild reducing agent
NaHSO3(aq). An excess of the stronger reducing
agent Zn(s) is required to convert V+5 to V +2, which
is then easily oxidized to V +3 by dilute (0.5%)
H2O2(aq).

Vanadium Oxidation States

HVO42-

VO(H2O)52+

V(H2O)63+

V(H2O)62+

2 HVO42(aq) + 3 Zn(s) + 14 H3O+(aq) + 8 H2O(l)

2 V(H2O)62+(aq) + 3 Zn(H2O)62+(aq)

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Vanadium Oxidation States

HVO42-

VO(H2O)52+

2 HVO42(aq) + HSO3(aq) + 7 H3O+(aq)

2 VO(H2O)52+(aq) + SO42(aq) + 2 H2O(l)

Vanadium Oxidation States

V(H2O)62+

V(H2O)63+

2 V(H2O)62+(aq) + H2O2(aq) + 2 H3O+(aq)

2 V(H2O)63+(aq) + 4 H2O(l)

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Metal ions influence color

[Cr(H2O)6]3+ [Fe(H2O)6]2+ [Co(H2O)6]2+ [Ni(H2O)6]2+ [Cu(H2O)6]2+

d3

d6

d7

d8

d9

The d-orbital electron count influences

compound color

Metal ions influence color

[Mg(H2O)6]2+ [Al(H2O)6]3+ [Ca(H2O)6]2+ [Sc(H2O)6]3+ [Zn(H2O)6]2+

d0

d0

d0

d0

d10

No d electrons no color.
Full d orbitals no color.

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Ligands influence color

[Ni(H2O)6]2+
green

[Ni(en)(H2O)4]2+ [Ni(en)2(H2O)2]2+
green/blue

blue

[Ni(en)3]2+
purple

Whats responsible for these colors?

Color is a result of electron transitions

MO Theory revisited:
Recall our simple
molecular orbital
diagramit only
involved s and p
orbitals
Now, however, we
have d orbitals to
consider

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MO Theory - Part I
The d orbitals reach only a very
short distance from the
nucleus they are essentially
non-bonding orbitals

An octahedral dn complex has

(12+n) electrons to fill in. The
first 12 go in the bonding
orbitals.

MO Theory Part II
The movement of electrons between
these levels is the source of the
chemical properties of transition
metal complexes (color, magnetic
properties, reactivity).

n
ground state

excited state

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Chapter 19: Transition Metals

and Coordination Chemistry
19.1 Survey of transition metals
19.2 1st-row transition metals
19.3 Coordination compounds
19.4 Isomerism
19.5 Bonding in complex ions: The localized electron model
19.6 The crystal field model
19.7 The molecular orbital model
19.8 The biological importance of coordination complexes

Coordination Compounds
The real bulk of inorganic chemistry occurs in the
reactions of coordination compounds (or complexes).
A coordination compound contains a complex ion and
counter ion
Complex ion: a central metal ion surround by one or
more ligands
Counter ion: ion that balances the charge of a
complex ion to form a neutral compound

Ligands are ions or molecules that have an independent

existence: NH3, H2O, CO, 2,2-bipyridine (bpy), etc.

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Ligand: A neutral molecule or ion

having a lone pair that can be used to
form a bond to a metal ion
Typical Coordination Numbers

Fig 19.6

Cu+

2, 4

Mn2+

4, 6

Sc3+

Ag+

Fe2+

Au+

2, 4

Cr3+

Co2+

4, 6

Co3+

Ni2+

4, 6

Au3+

Cu2+

4, 6

Zn2+

4, 6

See Table 19.12

Lewis Acids and Bases

To understand how coordination compounds form, we
need to understand Lewis acids and bases
A Lewis acid is an electron pair acceptor
A Lewis base is an electron pair donor
Lewis acids and bases are different from Brnsted-Lowry
acids and bases in that they can describe aprotic species
(no acidic protons are donated/accepted).

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Some Lewis Acids and Bases

Molecules with an incomplete octet can act as Lewis
acids

acid

base

Metal cations act as Lewis acids

Co2+ + 6 H2O
acid

[Co(OH2)6]2+

base

Some Lewis Acids and Bases

A Lewis base can influence electron rearrangement in a
Lewis acid

acid

base

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Some Lewis Acids and Bases

A Lewis acid can expand its valence shell to accommodate
a Lewis base

acid

2 Fbase

Coordination Chemistry
Since metal cations can acts as Lewis acids, and ligands have
electron pairs to donateinorganic coordination compounds
are often formed by Lewis acid / base chemistry

d-block elements:

oxidation state

Mn+

M
ne
Mn+ + 6 Lqacid base

Transition metals readily

ionize, and can lose
multiple electrons
net charge

[Mn+L6](n-6q)
metal complex

Once they are ionized, metal ions tend to surround

themselves with electron pair donors (Lewis bases)

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Coordination compounds
What are some aspects of coordination compounds we
should understand?
Coordination number
Ligands
Isomers and chirality

Coordination Number

(the number of ligands around the central atom)

Coordination number is influenced by
the size of the central atom
the bulk (or lack thereof) of the ligands
electronic interactions between metal and ligand
Coordination numbers can vary widely
2 and 3 (rare); 4, 5, and 6 (most common); others

Polymetallic complexes are possible, too.

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Ligands
Ligands can bond in one or more sites on the metal ion:
1 (monodentate): NH3, CO, H2O, I, Cl, etc.
2 (bidentate): acac, bpy, en, dppe

3 (tridentate): dien

4, 5, 6 (polydentate): cyclam, Cp, 18-crown-6

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Chelates (chele/chela = claw)

EthyleneDiamineTetraAcetic acid (EDTA)

HOOC

H2
C

HOOC

H2
C

CH2

H2C
C
H2

COOH
C
H2

COOH

H2
C

H2 C
N

Mn+
n = 2 to 4

H2 C
C
H2

O
O
O

CH2
H2 C
O

Very strong 1:1 complexes with transition metals O

Metal cations are sequestered from solution

See Fig 19.8

Used for detoxification and as a preservative.

The ligands can have a dramatic influence on

a metal complexes properties
NH
H

N Fe

1
CN
CN

NH

vs.
H

N Fe

OH2
OH2

OH2

CN

[Fe(TACN)(CN)3]

2+

[Fe(TACN)(H2O)3]2+

unreactive

reactive

all electrons paired

four unpaired electrons

yellow

blue

iron oxidation state= +2

negative redox potential

iron oxidation state= +2

positive redox potential

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NH
H

N Fe

NH

CN
CN

N Fe

OH2
OH2

OH2

CN

iron oxidation state= +2

2+

iron oxidation state= +2

-1 (-3) = +2

+2 (0) = +2

iron oxidation state= total molecular charge S(ligand charges)

ligand charges: CN= 1
TACN= 0
H2O= 0
Since the metals are identical, the oxidation states are identical,
and only the ligands differ, the ligands must be responsible for
the differing properties.

Ligands and Isomers

When ligands are involved, you can get isomers:
cis- and trans- (square planar)

optical isomers (tetrahedral)

mer- and fac- (octahedral)

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Stereochemistry can dramatically

influence key properties
Anti-cancer agent

cis chlorides

NOT an anti-cancer agent

trans chlorides

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Origin of anti-cancer activity

Origin of anti-cancer activity

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Isomers (Preview)
2 or more chemical species with identical
composition but different properties

Naming
Coordination
Compounds

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Naming Coordination Compounds

1. Cation named before anion
2. Ligands named before metal ion
3. o is added to the end of anionic ligand names (chloro-,
bromo-, iodo-, etc.). Neutral ligands retain their name (except
H2O, NH3, CO, NO)

4. Use prefixes (mono-, di-, tri-, tetra-, penta- and hexa-) for the
number of simple ligands; (bis-, tris-, tetrakis-, etc. for multiple
complex ligands)
5. Metal oxidation state is denoted with roman numerals in
parentheses.
6. Ligands are named in alphabetical order
7. If the complex ion has a negative charge, add ate to the
metal name (vanadate, ferrate, etc.). Sometimes the Latin
name is used.

Naming Examples
[Co(NH3)5Cl]Cl2
pentaamminechlorocobalt(III) chloride
K3Fe(CN)6
potassium hexacyanoferrate(III)
[Fe(en)2(NO2)2]2SO4

bis(ethylenediammine)dinitroiron(III) sulfate

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Complex Ions and the Localized Electron Model

Bond Formation
Mn+

Metal Ion
(electron acceptor)
Unoccupied hybrid orbital

Ligand
(electron donor with a lone pair)

Mn+

Coordinate covalent bond

See pg. 958

Figs. 19.20
and 19.19

Hybridization (L.E.M.)
Linear: sp

Ag(CN)2-

Square planar: dsp2

Ni(CN)42-

No reliable way to predict

sq. planar vs. tetrahedral

Tetrahedral: sp3

CoCl42-

L.E.M. cant predict important

properties of complex ions, like
color or magnetism

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Chapter 19: Transition Metals

and Coordination Chemistry
19.1 Survey of transition metals
19.2 1st-row transition metals
19.3 Coordination compounds
19.4 Isomerism
19.5 Bonding in complex ions: The localized electron model
19.6 The crystal field model
19.7 The molecular orbital model
19.8 The biological importance of coordination complexes

The Crystal Field Model

Ligands produce an electrostatic field around the metal ion
d-orbital energies split in the electrostatic field

Electron occupancy of d orbitals depends on the magnitude

of splitting
Crystal field model does NOT explain complex geometry
or bonding
Why care?
CFM explains how color and magnetism can arise in
complex ions by considering the d orbitals of the transition
metal.

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Octahedral Complexes

Consider ligands as negative point chargesconsider

the location of the electrons in the orbitals, which will
repel the negative charges of the ligands.

Co(NH3)63+

Fig 19.21

dxy

d z2

d x2-y2

dyz

dxz

Close
overlap,
higher
energy

Ligands influence properties

The ligands on a metal complex influence the energy of
the d orbitals.
Orbitals that point directly at ligands (dz2 and dx2-y2) are
higher in energy.
Orbitals that point between ligands (dxy, dyz and dxz) are
lower in energy.
eg (dz2 and dx2-y2)

d
t2g (dxy, dyz, dxz)

The nature of
the ligands
affects this
difference

octahedral ligand field

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Orbital Energy Splitting

(in Octahedral Complexes)

Example:
Co3+ (3d6)

eg orbitals
eg orbitals

t2g orbitals

t2g orbitals

Weak Field

Strong Field

Figs 19.22 and 19.23

Transition Metal Ion Properties

Weak Field
eg orbitals

t2g orbitals

Strong Field
eg orbitals

t2g orbitals

Example:
Co3+ (3d6)

High spin compounds

yield maximum number
of unpaired electrons:
(Paramagnetic )

Low spin compounds

yield minimum
number of unpaired
electrons:
(Diamagnetic)

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Spectrochemical series
CN- > NO2- > en > NH3 > H2O > OH- > F- > Cl- > Br- > IStrong-field
ligands
Large

small

Weak-field
ligands

Example: Is [Fe(CN)6] 4- paramagnetic or diamagnetic?

Fe oxidation state: from ion and ligand charges,
(-4) (-6) = +2: Fe2+
Number of 3d electrons on Fe2+ : 8 2 = 6
CN- is a strong-field
ligand
[Fe(CN)6] 4- is
diamagnetic

eg orbitals

Strong Field

t2g orbitals

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Examples

d5 complex high spin

Examples

d5 complex low spin

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Examples

d1 - d3 complexes only one spin configuration

Examples

d8 d10 complexes only one spin configuration

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Why do we see the colors we doenergy is absorbed.

[Ti(OH2)6]3+ or [Ti(OH)6]3- ion
eg orbitals

eg orbitals

t2g orbitals

t2g orbitals

Ground electronic state

photon absorption

Excited electronic state

= photon energy = hn = hc/

= wavelength of absorbed light

(nm) = 119,626/(kJ mol-1)

Large small complex absorbs blue end of spectrum

Small large complex absorbs red end of spectrum
Visible spectrum width = 400 700 nm = 300 170 kJ mol-1

See Fig. 19.26

See Table 19.16

Absorbed Wavelength

Observed Color (complementary)

Greenish yellow

Yellow

Red

Violet

Blue

Green

Colored compounds used in tattoos:

[Link]

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Appears
dz2 dx2-y2

absorbs
green
increasing energy

dxy

dyz

dxz

G B I V
dz2 dx2-y2

absorbs
blue

hn
dxy

dyz

dxz

dz2 dx2-y2

absorbs
violet

hn
dxy

dyz

dxz

Tetrahedral Complexes
None of d-orbitals point
directly AT the ligands

Small orbital splitting

and splitting order is
reversed
tet = (4/9) oct
Energy

R O Y

hn

dxy

dxz
dz2

Fig 19.27

dyz

tet

dx2-y2

Always weak field, high spin.

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Example:

2-

Cl
Co

Cl
Cl

Cl

How many unpaired electrons are there in this complex?

(1) Determine the number of electrons on the metal ion:
CoCl42-: (-4) (-2) = +2 7 electrons on Co2+

Energy

(2) Fill electrons in d orbitals from bottom up

dxy

dxz
dz2

dyz

tet

dx2-y2

Square Planar and Linear Complexes

Fig 19.29

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is influenced by:
The Mn+ oxidation state
(M3+) > (M2+) > (M+)
Example,
=

Fe(II)(NH3)62+
12,800 cm-1

vs.

Fe(III)(NH3)63+
26,000 cm-1

The row in which Mn+ lies in periodic table

(3rd row) > (2nd row) > (1st row)

is influenced by:
The identity of the ligands
Example,
[Fe(II)L6]2+
L=
=

H2 O
8,900

CN
30,000

Cl
5,900 cm-1

Spectrochemical series

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The spectrochemical series

Ligands
I- < Br- <S2- < SCN- < Cl- < ONO- < N3- < F- < OH- <
C2O42- < O2- < H2O < NCS- < CH3C=N < py < NH3 < en
< bpy < phen < NO2- < PPh3 < CN- < CO
Metal ions
Mn2+ < Ni2+ < Co2+ < Fe2+ < V2+ < Fe3+ < Co3+ < Mo3+
< Rh3+ < Ru3+ < Pd4+ < Ir3+ < Pt4+

Ligands influence color

[Ni(H2O)6]2+

[Ni(en)(H2O)4]2+

[Ni(en)2(H2O)2]2+

[Ni(en)3]2+

Appears:

green

green/blue

blue

purple

Absorbs:

red

red / orange

orange

yellow

increasing dorbital splitting

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Weak vs. strong field ligands

If we need to fill the d orbitals with four
electrons, where does the fourth electron go?

Weak vs. strong field ligands

If we need to fill the d orbitals with four
electrons, where does the fourth electron go?

Pairing the electron

requires energy
pairing energy (P)

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Weak vs. strong field ligands

If we need to fill the d orbitals with four
electrons, where does the fourth electron go?
Occupying an eg
orbital requires
energy
d

Weak vs. strong field ligands

If we need to fill the d orbitals with four
electrons, where does the fourth electron go?

< P = Weak field

Examples:

[Cr(OH2)6]2+

> P = Strong field

[Cr(CN)6]4-

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Weak vs. strong field ligands

If we need to fill the d orbitals with four
electrons, where does the fourth electron go?

High-spin
Examples:

[Cr(OH2)6]2+

Low-spin
[Cr(CN)6]4-

Demo: Nickel Complexes

Ni(H2O)62+(aq) + 6 NH3(aq) Ni(NH3)62+(aq) + 6 H2O(l)
(octahedral)
(octahedral)
Ni(NH3)62+(aq) + 3 en(EtOH) Ni(en)32+ + 6 NH3(aq)
(octahedral)
(octahedral)
Ni(en)32+(aq) + 2 Hdmg(EtOH) + 2 H2O(l)
Ni(dmg)2(s) + 3 en(EtOH) + 2 H3O+(aq)
(octahedral)
(square planar)
Note: If any green precipitate forms, it is Ni(OH)2(s).

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Demo: Ammines
Cu(H2O)42+(aq) + 4 NH3(aq) Cu(NH3)42+(aq) +
4 H2O(l)
Spectator Ion: SO42

Ni(H2O)62+(aq) + 6 NH3(aq) Ni(NH3)62+(aq) +

6 H2O(l)
Spectator Ion: NO3
Co(H2O)62+(aq) + 6 NH3(aq) Co(NH3)62+(aq) +
6 H2O(l)
Spectator Ion: Cl

Chapter 19: Transition Metals

and Coordination Chemistry
19.1 Survey of transition metals
19.2 1st-row transition metals
19.3 Coordination compounds

19.4 Isomerism
19.5 Bonding in complex ions: The localized electron model
19.6 The crystal field model
19.7 The molecular orbital model
19.8 The biological importance of coordination complexes

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Classes of isomers
Fig 19.9

Coordination Isomers:
[Cr(NH3)5SO4]Br and [Cr(NH3)5Br]SO4
SO4

Br

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Fig 19.10

Linkage Isomers:
NO2- can bond to the
metal through one of the
oxygens or through the
nitrogen

yellow

red

[Co(NH3)5(NO2)]Cl2

Pentaamminenitrocobalt(III)
chloride

[Co(NH3)5(ONO)]Cl2

Pentaamminenitritocobalt(III)
chloride

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Stereoisomers:
3

Cis

Geometrical isomers
Cis = together

Trans = across, opposite

Trans

Fig 19.11

Chloride ligands

Cis

Trans

green

violet

Fig 19.12

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a facial isomer (fac) where

the three identical ligands
are mutually cis

a meridional isomer (mer)

where the three ligands
are coplanar

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Optical Isomers
Figure 19.15

Mirror image of hand

Objects that are not
superimposable
until you make a
mirror image are
called chiral.

Zumdahl: hands are nonsuperimposable mirror images

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Figure 19.16

Isomers I and II
for [Co(en)3]3+

Nonsuperimposable
mirror images!

Geometric Isomers not always Optical Isomers

3

[Co(en)2Cl2
Trans isomer

Achiral Complex

]+

Cis isomer

Chiral Complex

Fig 19.17

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Achiral Complex

Chiral Complex
(I and III are enantiomers)

Chiral Amino Acids

C
N

C
C
*

O
D-Alanine (unnatural)

C
*

O
C
O

L-Alanine (natural in proteins)

* denotes chirality center, where the C noted has

4 different substituents (-CH3, -H, -COOH, -NH2)

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BIOINORGANIC CHEMISTRY
TMs serve as the active site within many large biological
molecules.
Key is ability of TM metals to
Coordinate with and release ligands
Easily undergo oxidation and reduction
Human body contains only 0.01% TM by mass, divided
among 3d Cr, Mn, Fe, Co, Ni, Cu, Zn and 4d Mo. Nature has
used the most abundant TMs:
3d abundance >> 4d/5d.
Fe is most abundant 3d element and the most used
biologically.
Mo is the most abundant 4d/5d element.

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BIOINORGANIC CHEMISTRY
Functions of these trace metals:
Electron Carriers. TM have >1 stable oxidation state.
Oxidized form can pick up electrons; reduced form can
release electrons elsewhere as pH or other conditions
change.
Oxygen Carriers. TM have >1 stable CN. At different O2
partial pressures, can bind or release this metabolically
crucial small molecule.

Catalysts (Enzymes). Flexibility of both oxidation state

and CN allows TM to bond reactants close together,
allowing reaction under milder conditions than normal.
Critical for organisms, which must carry out all metabolic
reactions near STP.

Hemoglobin Molecule

Figures 19.33,19.36

Heme

Sickle cell anemia (importance of structure)

High-altitude sickness (how hemoglobin works)
Toxicity of CO and CN- (ligand strength)

49