You are on page 1of 30

1.

Coordination Compounds

2.
3.

Chem 17
UP Diliman
Institute of Chemistry

4.
6.
7.
8.
9.
10.
11.
12.
13.

References for the Images and Examples Used for this Lecture PPT:
a. Petrucci, General Chemistry 2010
b. Whitten, General Chemistry 2011

Alfred Werner (1866-1919)

Two

coordination compounds

[CoCl(NH3)5]Cl2.

A coordinate covalent bond is a pair of electrons from


a donor shared with an acceptor.

Coordinate covalent bonds frequently are formed in Lewis acidbase reactions.

[Co(NH3)6]Cl3 and [CoCl (NH3)5]Cl2


Differing reactivity with AgNO3.

[Co(NH3)6]Cl3

Compounds made up of simpler compounds are


called coordination compounds.
CoCl3 and NH3.

Coordination Compounds
Important terms
Nomenclature
Structures
Isomerism in Coordination Compounds
Structural (Constitutional) Isomers
Stereoisomers (Geometric, Optical Isomerism)
Bonding in Coordination Compounds
Electronic Configuration of Metal Cations and Hybrid
Orbitals Concept
Crystal Field Theory
Color and the Spectrochemical Series
Kinetics of Ligand Exchange
Electrochemistry of Complexes
Other Applications

An example of a coordinate covalent bond is the one


formed between ammonia and borontrifluoride. The
e- which became shared between N and B came from
N.

.
H3N . + BF3

.
H3N . BF3

The complex formation below also shows formation of a coordination compound

Ag 2 NH 3 [ Ag ( NH 3 ) 2 ]
4

The ammine complexes contain NH3


molecules bonded to metal ions by
coordinate covalent bonds , e.g., [Cu(NH3)4]2+.
Dilute aqueous NH3 reacts with metal ions to
form the insoluble metal hydroxides or
hydrated oxides.

For example, Cu and Fe both react with


aqueous ammonia to form hydroxides.
Cu 2aq 2 NH3aq 2 H 2 O Cu(OH) 2 s 2 NH 4 aq
Fe2aq 3 NH3aq 3 H 2 O Fe(OH) 3s 3 NH 4 aq
However, in excess NH3 or highly concentrated NH3, the Cuhydroxide precipitate dissolves while the Fe(III)-hydroxide
does not.

The exceptions to this trend are metals that form


strong, water soluble hydroxides.

Group IA cations and the heavier Group IIA cations, Ca2+,


Sr2+, and Ba2+.

Certain hydroxides (e.g. Zn, Al) dissolve in


excess,highly concentrated hydroxide solutions.
Zn 2aq 2OH -aq Zn(OH) 2s

Zn(OH) 2 s 2OH- Zn(OH) 4

2-

aq

Several metal hydroxides dissolve in excess


aqueous NH3 to form ammine complexes.

2
Cu(OH) 2 s 4 NH3aq Cu(NH 3 ) 4 aq 2 OHaq
Co(NH ) 2 2 OH
Co(OH) 6 NH
2 s

3 aq

3 6

aq

aq

Some metal ions that form soluble ammine


complexes with an excess of aqueous NH3
include Co2+, Co3+, Ni2+, Cu2+, Ag+, Zn2+,
Cd2+, Hg2+

A ligand is a Lewis base that coordinates to


a central metal atom or ion.
A donor atom is the atom in a ligand that
donate a lone pair of electrons to form a
coordinate covalent bond.
A unidentate ligand is a ligand that can bind
through only one atom (i.e. only one donor
atom attached to the metal)
A polydentate ligand (chelating agent)
provides several donor atoms that can
coordinate simultaneously with the metal
ion.
8

Ion/
Molecule

Name

Name as a
Ligand

NH3

ammonia

ammine

CO

carbon monoxide

carbonyl

Cl-

chloride

chloro*

Ion/Molecule

Name

Name as a
Ligand

CN-

cyanide

cyano

CO3-2

carbonate

carbonato

OHS2SO42SCN-

hydroxide
sulfide
sulfate
thiocynate

hydroxo
sulfido
sulfato
Thiocynato-S
Thiocynato-N

Other halides can also be ligands: e.g. fluoro, bromo, iodo


9

Ion/Molecule
CO
NO

Name
Carbon dioxide
Nitrogen
monoxide

NO2-

nitrite

ONOPH3

nitrito
phosphine

Name as a
Ligand

10

A polydentate ligand is a ligand that can bind


through more than one donor atom.
There are known examples of bidentate, tridentate,
quadridentate, quinquedentate, and sexidentate
ligands.

Carbonyl
Nitrosyl

Nitro
Nitrito-N
Nitrito-O
Phosphine

Chelate complexes are complexes that have a


metal atom or ion and polydentate ligand(s)
that form rings.

(en) = ethylenediamine
is an example of a
bidentate ligand
11

12

Petrucci

ox

Co2+

ox

Co(ox)2 2
A square planar
complex

13

Coordination compound/complex: Metal ion


bonded with ligands (ions or molecules).

The coordination number is the number of donor


atoms coordinated to a metal atom or ion.

Most common: 4 and 6; Tetrahedral, Square Planar, Octahedral

14

Example: For the complex compound


Na3[Co(Cl)6] the coordination number is
_________, and the coordination sphere is
_______. The oxidation state of Co is ____.

You do it!

A coordination sphere includes the metal atom or


ion and the ligands coordinated to it. The
coordination sphere does NOT include
uncoordinated counter ions (i.e. the

For the complex compound K3[Co(Cl)6] the


coordination number is 6 , and the
coordination sphere is 7 . The oxidation state
of Co is +3.

corresponding cation or anion outside of the


bracket).

15

16

Example: For the complex compound


Ca[Zn(OH)4] the coordination number is
_________, and the coordination sphere is
_______. The oxidation state of Zn is ___.

Cations are named before anions.

1.

Coordinated ligands are named in alphabetical


order.
Prefixes that specify the number of each kind of
ligand (di = 2, tri = 3, tetra = 4, penta = 5, hexa
= 6, etc.) are NOT used in alphabetizing

2.

You do it!

However, prefixes that are part of the name of the


ligand, such as in (CH3CH2)2NH:, diethylamine, are
used to alphabetize the ligands.

For the complex compound above, the


coordination number is 4 , and the
coordination sphere is 5 . The oxidation state
of Zn is +2.
17

For complicated ligands, especially those


that have a prefix such as di or tri as part of
the ligand name, these prefixes are used to
specify the number of those ligands that are
attached to the central atom.

3.

4.

18

The names of most neutral ligands end in


the suffix -o.

4.

Examples of ligands ending in o are:

bis = 2; tris = 3; tetrakis = 4; pentakis = 5


hexakis = 6.

Examples:
[Fe(en)3]+3 is Tris(ethylenediamine)iron(III) cation.
[Co(ox)(en)2]+1 is Bis(ethylenediamine)oxalatocobaltate(III) anion
19

ClS2O2OHCNNO3SO42-

chloro
sulfido
oxo
hydroxo
cyano
nitrato
sulfato

[PdClBr(OH)2(en)] is Bromochloroethylenediaminedihydroxopalladium(IV)
complex, a neutral ligand.
20

The names of most neutral ligands are


unchanged when used in naming the
complex.

5.

6.

There are several important exceptions to this


rule including:

NH3
H2O
CO
NO
CS

7.

ammine
aqua
carbonyl
nitrosyl
thiocarbonyl

The oxidation number of a metal that exhibits


variable oxidation states is designated by a
Roman numeral in parentheses following the
name of the complex ion or molecule.
If a complex is an anion, the suffix "ate" ends
the name.

No suffix is used in the case of a neutral or cationic


complex.
Usually, the English stem is used for a metal, but if this
would make the name awkward, the Latin stem is
substituted.

Ferrate instead of ironate


Plumbate instead of leadate
Argentate (Ag), Aurate (Au)
Cuprate (Cu)

Others:

[Pt(OH2)2CO(en)NO] is Diaquacarbonylethylenediaminenitrosylplatinum(IV)
complex, a neutral ligand.

Platinate (Pt), Palladate (Pd), Titanate, Vanadate,


Antimonate, Tungstate, Hafnate, Zirconate, etc.

21

Name the following compounds:


Na3[Fe(Cl)6]
sodium hexachloroferrate (III)

22

Write formulas for the following compounds:


potassium hexacyanochromate(III)
K3[Cr(CN)6]
tris(ethylenediammine) cobalt(III) nitrate
[Co(en)3] (NO3)3

[Ni(NH3)4(OH2)2](NO3)2
tetraamminediaquanickel(II) nitrate

23

24

Fluoro
Chloro
Bromo
Iodo
Azido
Cyano
Thiocyanato

FClBrIN3CN*SCN-

Now: Thiocynato-S

Isothiocyanato *NCS Now: Thiocynato-N

Hydroxo
Ammine
Methylamine

OHNH3
H3CNH2

Phosphine (phosphane)
Pyridine

Common

Aqua
H 20
Carbonyl
CO
Thiocarbonyl
CS
Nitrosyl
NO
Nitro (or Nitrito-N) NO2Nitrito-O
ONO(O-bonded)
Nitrato
NO3Amido
NH2Sulfato
SO4-2

25

Give the names for the following:


1.
[Cu(NH3)4](NO3)2
2.
Ba[PtCl4]
3.
(NH4)4[Mn(CN)6]
4.
[CoN3(NH3)5]SO4
5.
Na[AlCl4]
6.
Rb3[AgF4]
7.
[FeBrCl(en)2]Cl
8.
[Fe(H2O)4(OH)2]Br

Chelating Ligands

Chelates which may have two or more points of attachments to


the metal atom.
Nitrato
Oxalato
C2O4-2
Ethylenediammine;
en
NH2CH2CH2NH2 (a bidentate)
Diethylenetriammine;
dien NH2CH2CH2NHCH2CH2NH2
Triethylenetetraamine;
trien NH2(CH2)2NH(CH2)2NH (CH2)2NH2
Ethylenediaminetetraacetate,
EDTA
2,2-bipyridine;
bipy
1,10-phenanthroline;
phen
Dimethylglyoxime,
DMG
26

27

PR3
py

Sodium tetrahydroxozincate(II)
Dichlorobis(ethylenediammine)cobalt(III) Nitrate
Triaquabromoplatinum(II) Chloride
Potassium trioxalatochromate(III)
Sodium pentacyanomanganate(IV)
Ammonium
diamminetetraisothiocyanochromate(III)
Tetraamminedinitroplatinum(IV) bromide
Hexammineruthenium(III) tetrachloronickelate(II)
Trans-diamminedinitroplatinum(II)
Tri-aqua-cis-dibromochlorochromium(III)
28

Coordination Chemistry
Molecular Geometries
Isomerism in Complexes

The structures of coordination compounds


are controlled primarily by the coordination
number of the metal.
Usually the structures can be predicted by
VSEPR theory (See GenChem books).
The geometries and hybridizations for common
coordination numbers are summarized in the
following table.

30

Petrucci

Coordinati
on Number

Geometry

Metal Hybridization

Example

linear

sp

Ag[NH3)2]+

tetrahedral

sp3

[Zn(CN)4]2-

square planar

dsp2 or sp2d

[Ni(CN)4]2-

trigonal bipyramid

dsp3

[CuCl 5 ]-3
Fe(CO)5

Square pyramidal

d2sp2

octahedral

d2sp3 or sp3d2

[Ni(CN)5]3-

Structure of some complex ions

[Co(en)3]+3
[Fe(CN)6]431

General Chemistry: Chapter 24

Copyright 2011 Pearson


Canada Inc.

Sli
de
32
of
53

Isomers:

Structural
(constitutional)

Differ in their structure and properties but with


similar molecular weight (or formula mass).

Stereoisomerism
(configurational)

Structural isomers:
Differ in basic structure.

1. Ionization
2. Hydrate
3. Linkage
4. Coordination

Stereoisomers:
Same number and type of ligands with the same
mode of attachment, but differ in the way the
ligands occupy space around the metal ion.

1. Geometric
a. Cis-trans
b. Fac-mer
2. Optical
-has mirror image
which are not
superimposable

34

2. Configurational (Stereo) Isomerism:

1. Structural*** isomerism:

Stereoisomers which have the same types of ligands but


have different geometric arrangement.

Have the same overall formula but have different


ligands attached to the central atom or ion

2.1 Diastereomers
** Conformational isomers (identical
bonding but have different bends or twists)
**
Geometric isomers
Example: Cis vs. Trans isomers
Fac vs. Mer isomers

1.1 Ionization isomers


1.2 Hydrate or solvent isomers
1.3 Coordination isomers
1.4 Linkage Isomerism.
***also known as Constitutional isomerism

2.2 Enantiomers (Optically active)

(Chiral, non-superimposable mirror images).

35

36

Example of Structural (constitutional) Isomerism

1.1. Ionization or Ion-Ion Exchange Isomers

[Pt(NH3)4Cl2]Br2
H3 N
H3 N

Cl
Pt

+2
2-

N H3

Cl

* Hydrate isomers are a special case of ionization


isomers in which water molecules may be
changed from inside to outside the coordination
sphere.

[Pt(NH3)4Br2]Cl2
H3 N

N H3

H3 N

Counter ions
are Br-.

Br
Pt+4
Br

N H3

+2
2-

N H3

For example:

[Fe(OH2)6]Cl3 vs.[Fe(OH2)5Cl]Cl2 H2O

.
[Fe(OH2)4Cl2]Cl2 2H2O

Counter ions
are Cl-.

37

[Cr(OH2)6]Cl3

OH2
H2 O
H2 O

Cr
OH2

[Cr(OH2)5Cl]Cl2. H2O
3+
OH

OH

Counter ions
are 3 Cl-.

OH2
H2 O
H2 O

Cr
OH2

38

[Cr(OH2)5Cl]Cl2. H2O

[Cr(OH2)6]Cl3
2H2O

2+

OH2

Cl

H2 O
H2 O

OH

OH2

OH

Counter ions
are 3 Cl-.

Counter ions
are 2 Cl- and
1 water.

Note whether the water molecule(s) are inside or outside


the coordination sphere.

Cr

3+
OH

39

OH2
H2 O
H2 O

Cr
OH2

[Cr(OH2)4Cl2]Cl2.

2+
Cl
OH

Counter ions
are 2 Cl- and
1 water.

OH2
H2 O
H2 O

Cr
OH2

1+
Cl
Cl

Counter ions
are 1 Cl- and
2 waters.

40

10

[Co(NH3)5ONO]Cl2

* Coordination isomers denote an exchange


of ligands between the coordination spheres
of the cation and anion.
H3 N
H3 N

Pt

4 -

Cl

4 +
N H3

Cl

N H3

Cl

Pt
Cl

[Pt(NH3)4][PtCl6]

Cl

H3 N

Cl

H3 N

Cl
Pt
Cl

Nitrito -O

2 -

2 +
N H3

Cl

N H3

Cl

Cl
Pt

H3 N
H3 N

Cl

[Pt(NH3)4Cl2][PtCl4]

N H3

Nitrito-N

2+

N H3
Co O

[Co(NH3)5NO2]Cl2

H3 N

N
O

Counter ions are


2 Cl-.

H3 N

N H3
Co N
N H3

2+
O
O

Counter ions are


2 Cl-.

Note which atom in the ligand is bound to the central metal atom.
Another example: SCN- ligand can bind either through S or N.

The isomeric distinction is whether the ligands are on the


cation or the anion.
41

Petrucci FIGURE 24-4

42

Ionization
Isomerism
[CrSO4(NH3)5]Cl
pentaaminesulfatochromium(III) chloride

[CrCl(NH3)5]SO4
pentaaminchlorochromium(III) sulfate

Coordination Isomerism
Nitrite ion
Linkage

[Co(NH3)6][CrCN6]
hexaaminecobalt(III) hexacyanochromate(III)

isomerism illustrated

[Cr(NH3)6][CoCN6]
The nitrite ion can bind through the nitrogen lone pair or the oxygen lone pair.
(a) Pentaamminenitrito-N-cobalt(III) cation.
(b) Pentaamminenitrito-O-cobalt(III) cation.

hexaaminechromium(III) hexacyanocobaltate(III)

11

[Co(H2O)5Cl]Br2

[Pt(CO)4Br2]* [PtI4]* *+/-2

[CuCl4(NO2)]3-

[Cr(CH3NH2)4Cl2]Br

Stereoisomers are isomers that have different


spatial arrangements of the atoms relative to the
central atom.
Complexes with only simple ligands can occur
as stereoisomers only if they have coordination
numbers equal to or greater than 4.

45

46

H3N

Geometrical isomers are stereoisomers that are


not optical isomers.

H3N

Cl
Pt
Cl

H3N
Cl

Cl
Pt
N H3

cis- [Pt(NH3)2Cl2] trans-[Pt(NH3)2Cl2]

Example: Cis-trans isomers


have the same kind of ligand either adjacent to each
other (cis) or on the opposite side of the central metal
atom from each other (trans).

Take note of where


the ligands are
positioned relative to
the central atom.
The geometric isomers of[PtCl2(NH3)2]
47

12

Other types of isomerism can occur in


octahedral complexes.
Complexes of the type [MA2B2C2] can occur in
several geometric isomeric forms:
trans- trans- trans cis- cis- cis cis- cis- trans-

FIGURE 24-5
Sli
de
49
of
53

Geometric Isomerism - illustrated


General Chemistry: Chapter 24

Copyright 2011 Pearson


Canada Inc.

50

Facial versus Meridional Isomers of


[Co(NH3)F3]

(NH
F 3)`

(NH3)`
F

(NHF
3)`
F
(NH3)`

F
Se
F
F3)`
(NH

FIGURE 24-6

Cis and trans isomers of an octahedral complex


General Chemistry: Chapter 24

Copyright 2011 Pearson


Canada Inc.

Sli
de
51
of
53

F
Se
F

(NH
F 3)`
octahedral
Meridional

octahedral
Facial
52

13

The geometric
isomers of

[Ma3b3c3]n complex

trans-diammine-trans-diaqua-trans-dichlorocobalt(III) ion

[CoCl3(NH3)3],
A [Ma3b3]n type of
complex

Geometric isomers

The 3 green balls Cl are


facing the same side (i.e.
have a common quadrant).

N H3
Cl
H2O
Co
Cl
O
N H H2

All trans

The 3 green balls Cl are


on the same plane (i.e. on
adjacent quadrants).

Same type of ligands are all position opposite to each other

54

Geometric isomers
trans-diammine-cis-diaqua-cis-dichlorocobalt(III) ion

N H3
Cl
H2O
Co
O
H2
Cl
NH3

N H3
Cl
Co
H2O
Cl
NH3

H2O
Cis H2O

Cis Cl

Trans NH3
55

56

14

Geometric isomers

Geometric isomers

cis-diammine-cis-diaqua-trans-

cis-diammine-trans-diaqua-cis-

dichlorocobalt(III) ions

dichlorocobalt(III) ions

Cl

NH3 H O Cl NH3
2
Co
Co
O
H2
N H3 H2O
N H3
Cl
Cl

H2O

OH2

Cl
Cl

Cis NH3

NH3

Co
NH
O H2 3

Cl
Cl
Cis Cl

Trans Cl

OH2

NH3

Co
NH
O H2 3
Trans H2O

Cis NH3

Cis H2O
57

58

The phenomenon of rotation of polarized light is called optical


activity.

Light from an ordinary source consists of electromagnetic waves vibrating in all


planes; it is unpolarized.
This light is passed through a polarizer, a material that screens out all waves
except those vibrating in a particular plane.
The plane of polarization of transmitted polarized light is then changed by
passage through an optically active substance.
The angle through which the plane of polarization has been rotated is determined
by rotating an analyzer (a second polarizer) to the extent that all the polarized light isSli
de
59
absorbed.
General Chemistry: Chapter 24

Copyright 2011 Pearson


Canada Inc.

of
53

Racemic mixture: separate equimolar solutions


of the two isomers (i.e. the mirror images of a
complex) rotate plane polarized light by equal
angles but in opposite directions. Net rotation =
zero!

L (left)

D (right)

However, if the concentrations of the D and L compounds present in a


mixture are different, there would be a net rotation.
60

15

2.1 Optical Isomers/ Enantiomers are


stereoisomers with optical activity
Tetrahedral complex which does
NOT have a chiral center, is
superimposable to its mirror image.
E.g. [CoCl2(CO)(NH3)]2+
mirror

Square Planar
complex with 4
different ligands
(e.g.
[PtBrClF(OH)]2-

When the
mirror image
is flipped
sideways, it
becomes
identical to
the original
image

61

62

63

64

16

65

66

Mirror images are superimposable:


Non - enantiomers
1. /2 twice

A1

A2

Stereoisomer 1

Mirror Image of
Stereoisomer A1

2. 2

If you rotate A2 (along horizontal plane), and then invert along the
z-axis, the resulting structure will be superimposable to A1.
Theres a horizontal plane of symmetry which reflects the bottom
half to the upper half.
67

68

17

Mirror images are superimposable:


Stereoisomer 2

Stereoisomer 1

1. /2 twice

A4

A3

Mirror Image of
Stereoisomer A3

Stereoisomer 2

Both stereoisomers are superimposable to


their mirror images; both are NOToptically active.

If you rotate A4 (along the horizontal plane), the resulting structure


will be superimposable to A3, thus, A3 and A4 are identical !!!
Molecule A3 could be divided into two by a vertical mirror plane (as
indicated by the yellow arrow above.)
69

mirror images of each other but are NOT


superimposable; therefore, enantiomers
A5

A6

Stereoisomer

Mirror Image of
Stereoisomer A5

If you rotate A6 horizontally (along xy-plane), then rotate


the resulting structure along the x-axis, the resulting
final structure is not superimposable to A5
71

70

Formula

# Stereoisomers

Pairs of enantiomers

Ma6

Ma5 b1

Ma4 b2

Ma3 b3

Ma4 bc

***Ma3 bcd

Ma2 bcde

15

Mabcdef

30

15

***Ma2b2c2

Ma2b2cd

***Ma3b2c

0
72

18

Draw the unique stereoisomers of the following


and look for enantiomers.

bonding in a complex to be an

electrostatic attraction between a positively


charged nucleus and the electrons of the
ligands.

[Cr(en)(NH3)2(OH2)2]+3

4 stereoisomers two of which are


non-superimposable images.

Consider

en

Electrons on metal atom repel electrons on ligands.


The focus of CFT is particularly on the effect of the
incoming ligands on the d-electrons of the metal
ion.
The energy of the d-orbital electrons will be affected
depending on the type of orbital (e.g. dxy, dxz, dyz,
dx2-y2, dz2). Some would be destabilized, some would
not be directly on the path of the ligands, hence not
affected.

[Cr(en)2(H2O)Cl]+2

73

Approach of six ligands to a metal ion to form a


complex ion with octahedral structure. The octahedral
field affects the metal through the x-y-z axes.

Approach of six ligands to a metal ion to form a


complex ion with octahedral structure. The octahedral
field affects the metal through the x-y-z axes.

dxy

Maximum repulsion occurs with the dz and dx2-y2 orbitals, and


their energies are raised.
Repulsions with the other d orbitals are not as great. A difference
in energy results between the two sets of d orbitals. Copyright 2011 Pearson

Imagine a potential head-on collision of the electrons from the ligands with the
d-electrons of the metal. The octahedral field would not affect directly the xy, yz
and xz lobes.

General Chemistry: Chapter 24

Canada Inc.

dyz

dxz

Sli
de
75
of
53

Repulsions with the other d orbitals are not as great. A difference in


energy results between the two sets of d orbitals.
Copyright 2011 Pearson
General Chemistry: Chapter 24

Canada Inc.

Sli
de
76
of
53

19

eg

t2g
Petrucci

d orbitals
before splitting

Some ligands would have STRONG interaction with the


metal, while others would have WEAK interaction.

Strong field ligands would have greater o separation


between the t2g and eg orbitals. The crystal field stabilization
energy is much larger.

Weak field ligands would have lower o separation, and a


smaller crystal field stabilization energy.

d orbitals under
an octahedral field

Splitting of thed-orbital energy levels in the formation of an


octahedral complex ion results to two types of orbitals: three t2g and
two eg orbitals.
FIGURE 24-12

The O is the corresponding energy separation (i.e. crystal field


stabilization energy).
Copyright 2011 Pearson
General Chemistry: Chapter 24

Canada Inc.

Sli
de
77
of
53

78

26

1s
Large 0
Strong field ligands

Fe

26

2
2

2s 2 p

3s 2 3 p 6
CN- , CO > NO2- > en > py NH3 > EDTA4- > SCN- > H2O >
ONO- > ox2- > OH- > F- > SCN- > Cl- > Br- > ISmall 0
Weak field ligands

4s

d6
3d

Take note where the


electrons are taken off when
you are making the cations
(the outermost shell first,
from 4s before 3d)

Fe 2

1s 2
2s 2 2 p 6
3s 2 3 p 6
4s
26

d6
3d

Fe 3

1s 2
2s 2 2 p 6
3s 2 3 p 6
4s 0

d5
3d
80

20

27

Co

1s

27

2
2

2s 2 p

3s 2 3 p 6
4s

Co 2

28

1s 2

d7

2s 2 p
3d

4s

2s 2 p
4s

4s

d6
3d

29

1s 2
2

2s 2 p

3s 2 3 p 6
1

4s

d10
3d
Instead of

4s2d9

Copper is one of those


exception, the filled dorbital is more stable, hence
one e- from 4s is promoted
to the originally last halffilled 3d orbital

2s 2 p

3s 2 3 p 6

3s 2 3 p 6

d10

3s 2 3 p 6

3d

28

Ni 4

1s 2

d6

2s 2 2 p 6

3d

3s 2 3 p 6
0

82

d5
3d

4s 0

3d

4s 0
29

d8

2s 2 2 p 6

Fe 3

2s 2 2 p 6

1s 2

1s 2

4s

81

Cu 1

Ni 2

4s

Take note where the


electrons are taken off when
you are making the cations
(the outermost shell first,
from 4s before 3d)

26

Cu

3d

1s 2
29

d8

3s 2 3 p 6

Take note where the


27 Co
electrons are taken off when
1s 2
you are making the cations
2s 2 2 p 6
(the outermost shell first,
from 4s before 3d)
3s 2 3 p 6

28

2
2

3d

3s 2 3 p 6

1s

d7

Ni

Very large O

Cu 2

1s 2
2s 2 2 p 6
3s 2 3 p 6

d9

Small O

[FeCl6]3-

[Fe(en)3]3+

3d

4s 0
83

84

21

27

Co 3

1s 2
2

2s 2 p

3s 2 3 p 6
E
N
E
R
G
Y

d6

d-orbital splitting of Co3 + in


an octahedral field

Crystal field splitting of the d-orbitals for a


metal ion under a tetrahedral field

3d

4s 0

Both t2g and eg orbitals are occupied

The Td denotes the energy separation of the lower two eg orbitals


and the upper three t2g orbitals of the tetrahedral complex. The
energy separation is small, so the effect of the field strength of the
ligand is not considerable. ALL complexes are high-spin (i.e the
upper ones are occupied first before there is e- pairing).

The 2 eg orbitals are empty

General Chemistry: Chapter 24

27

Co 2

1s

2
2

2s 2 p
3s 3 p
4s 0

3d

d7

Both t2g and eg orbitals are


occupied, no matter what the
field strength of the ligand is,
since the energy difference
between these two types of
orbitals is just small (Td << o)

[CoCl4]2-

eg

Sli
de
86
of
53

t2g
Most destabilized

t2g

e
g
[Co(NH3)4 ]2+

Copyright 2011 Pearson


Canada Inc.

Least destabilized
87

88

22

(a) Splitting of the d energy level in a square-planar complex can be related


to that of the octahedral complex.
(b) There are no ligands along the z axis in a square-planar complex, so we
expect the repulsion between ligands and dz2 e- to be much less than in an
octahedral complex. The energy level is lowered considerably from that in
an octahedral complex.
(c) The energy levels of the dxz & dyz orbitals are lowered slightly because the
e- in these orbitals are concentrated in planes perpendicular to that of the
square-planar complex.
(d) The energy of the dx2-y2 orbital is raised because the x and y axes
represent the direction of approach of 4 ligands to the central ion.
(e) The energy of the dxy orbital is also raised because this orbital lies in the
plane of the ligands in the square-planar complex.

Crystal field splitting in a square-planar and an


octahedral complex

FIGURE 24-14

General Chemistry: Chapter 24

Copyright 2011 Pearson


Canada Inc.

Sli
de
89
of
53

(f) The energy difference between the dxy and dx2-y2 orbitals in a squareplanar complex is the same as in an octahedral complex because these
orbitals are equally affected by ligand repulsions in both complexes.
90

Pd(II) and Pt(II) complexes : Example : [ PtCl 4 ]2 ;[ Pd (CO)4 ]2

Coordination 4 complexes with " bulky"ligands :


Example : [Co(en) 2 ]2 ;[ FeBr2 (ox)]2

Many Ni2+ complexes

28

d8

Ni 2

1s 2

d-orbital
splitting
under a
square
planar CF

2s 2 2 p 6
2

Ni
NO2

NO2

3s 3 p

[ Ni( X )4 ]n

3d

4s 0

e
g

If d8 and paramagnetic

t2g versus

[ Ni(ox)( NO2 )2 ]

91

Tetrahedral

Square Planar

92

23

If d6 and magnetic
[ Fe A3 B3 ] property is given

eg
versus

t
II

[ PtAx By ]n

2g

Low Spin Octahedral, with


Strong Field Ligands
diamagnetic

High Spin Octahedral,


with Weak Field Ligands
paramagnetic

e
g
t



If tetrahedral, the
complex is also
paramagnetic

2g

versus

Octahedral, with either


Strong or Weak Field
Ligands is Paramagnetic

Square Planar d-8


complexes are
Diamagnetic

93

hc

94

Primary colors:

red

green

blue

Red (R), green (G) and blue (B).

Secondary colors:

Complementary colors:

Produced by mixing primary colors.

Shorter
wavelength,
;
Higher
Frequency,
Higher Energy

Secondary colors are complementary to primary.


Cyan (C), yellow (Y) and magenta (M)
Adding a color and its complementary color
produces white.

Longer
wavelength, ;
Smaller Frequency,
Lower Energy

Cyan (C), yellow (Y) and magenta (M)


95

24

orange

red

yellow

The mixing of
colors

indigo

General Chemistry: Chapter 24

[CoCl4]-

[Co(NH3)6]2+

Copyright 2011 Pearson


Canada Inc.

green

indigo

The secondary colorsyellow (Y), cyan (C), and magenta (M)are produced in
regions where two of the beams overlap. The overlap of all three beams produces
white light (W).

blue

Sli
de
97
of
53

A weak field ligand, would absorb


lower energy wavelengths (e.g. R-OY), while strong field ligands would
absorb at higher energies (e.g. VIBG)
A complex which would light
corresponding to the red-region
would appear green.
A complex absorbing at very low
wavelengths (near ultraviolet region)
would appear yellow green.
A compound absorbing within the
yellow-to-green wavelength (region)
would appear purple.
98

[CoCl4]= absorbs in the


yellow region of the
spectrum and transmits
blue light.
[Co(NH3)6]2+ absorbs in the
blue region of the spectrum
and transmits yellow light
(appears straw yellow)

LIGHT Absorption and transmission

red

orange

yellow
indigo
indigo

green
blue

Red-shift
Cl is a weaker field
strength ligand than H2O
Blue-shift
NH3 is a stronger
field ligand than H2O

25

Cl- > Br- > IZn2+(aq) + 4 NH3(aq) <==> [Zn(NH3)4]2+(aq)


Kf =

[[Zn(NH3)4]2+]
= 4.1108
[Zn2+][NH3]4

Suppose 1.0 M Zn(NO3)2 is dissolved in


excess 2.5 M NH3, what is the resulting
equilibrium concentration of the
tetrazinc(II) complex?
red
indi
go
indi
go

oran
ge

blu
e

yell
ow

gre
en

Effect of ligands on
24-18 of
the FIGURE
colors
coordination
compounds

General Chemistry: Chapter 24

Copyright 2011 Pearson


Canada Inc.

Sli
de
10
1
of
53

Set up the ICE TABLE to find the equilibrium concentrations.


[Zn(NH3)4]2+(aq) <==> Zn2+(aq) + 4 NH3(aq)
Initial [ ]
Change [ ]

1.0 M
-x

____
+x

2.5 M
+ 4x

What is the pH of a 0.10 M


[Cu(NH3)4]Cl2(aq) solution?
pH > 7, pH =7, pH < 7

26

CuSO4 in concentrated HCl(aq).


[CuCl4]2-

Fast[Cu(H O) ]2+ + 4 NH

[Cu(NH3)4]2+ + 4 H2O

Fast

[CuCl4]2-

[Cu(H2O)4]2

[Cu(NH3)4]2+

Labile complex ions

[Cu(H2O)4]2+

+4

Cl-

[Cu(Cl)4]2-

+ 4 H2O

The exchange of ligands in the coordination sphere of Cu 2+ occurs very rapidly.

Water is said to be a labile ligand.

The solution at the extreme left is formed by dissolving CuSO 4 in concentrated


HCl(aq). Its yellow color is due to [CuCl4]2-.

Slow reactions (often monitored by color


change) are caused by non-labile ligands.

When a small amount of water is added, the mixture of [Cu(H2O)4]2+ and [CuCl4]2ions produces a yellow-green color.
When CuSO4 is dissolved in water, a light blue solution of [Cu(H2O)4]2+ forms.

Fast reactions can operate at the diffusion limit.

FIGURE 24-20

NH3 molecules readily displace H2O molecules as ligands and produce deep blue
[Cu(NH3)4]2+ (extreme right).
General Chemistry: Chapter 24

Copyright 2011 Pearson


Canada Inc.

Sli
de
10
6
of
53

Inert complex ions

trans-CrCl2(H2O)4+.

Blue shifted due to


exchange of Cl- and H2O

The green solid CrCl36 H2O produces the green


aqueous solution on the left.
The color is due to trans-CrCl2(H2O)4+.
A slow exchange of H2O for Cl- ligands leads to a
violet solution of Cr(H2O)63+ in one or two days
(right).
General Chemistry: Chapter 24

Copyright 2011 Pearson


Canada Inc.

Sli
de
10
7
of
53

27

Co3+(aq) + e- Co2+(aq)
4

Co3+(aq)

+ 2 H2O(l) 4

Co2+(aq)

Co3+(aq) + e- Co

E = +1.82 V
+4

H+

+ O2(g)
Ecell = +0.59 V

E = +1.82 V

[Co(NH3)6]3+(aq) + e- [Co(NH3)6]2+(aq) E = +0.10 V


[Co(en)3]3+ + 3e- Co + 3(en) E = ?

But:

Co3+(aq) + NH3(aq) [Co(NH3)6]2+(aq) Kf = 4.51033

[Co(en)3]3+ Co3+ +3(en) G = -RTln(1/Kf)

and

Co3+ + 3e-

[Co(NH3)6]3+(aq)

e-

[Co(NH3)6]2+(aq)

E = +0.10 V

Which is easier to reduce? Which has more


positive and larger magnitude of standard
reduction potential?

E = ?

B. [Co(NH3)6]3+ + 3e- Co + 3NH3)6 E = ?

3e- Co + 3(en) G = -zFE =

Stability of complexes with chelating ligands due


to the smaller negative entropy change when they
are formed.
G formation of [Cu(en)]2+ is more negative (i.e.
more spontaneous) and of greater magnitude than
[Cu(NH3)] 2+.

G formation H TS
Negative
Exothermic
Bond formation

CLUE: Which is more easily dissociated ?

Negative S

Gdissociation H TS

[Co(en)3]3+ or [Co(NH3)6]3+
Explain based on H;S,G, Kf or Kd and E.

G = -zFE =

Co+3 is even more stabilized if coordinated to chelating


ligands than to simple monodentate ligands.

Co+3 is more stabilized, and not easily reduced to


Co(0) if coordinated to ligands.

A. [Co(en)3]3+ + 3e- Co + 3(en)

[Co(en)3

]3+ +

11
1

Positive
Endothermic
Bond Breaking

Positive S

Chelated complex
has smaller
negative Sf

Favored if more
ligands will be
dissociated

28

Black and white.


Finely divided AgBr on modified cellulose.
Photons oxidize Br- to Br and reduce Ag+ to Ag.

Hydroquinone (C6H4(OH)2) developer:

Reacts only at the latent image site where some


Ag+ is present and converts all Ag+ to Ag.
Negative image.

Fixer removes remaining AgBr.

AgBr(s) + 2 S2O32-(aq) [Ag(S2O3)2]3-(aq) + Br-(aq)

Print the negative


General Chemistry: Chapter 24

Copyright 2011 Pearson


Canada Inc.

Sli
de
11
3
of
53

CONSULT YOUR LAB


EXPERIMENTAL RESULTS

Tetrasodium EDTA

FIGURE 24-25

e.g. For sequestration of heavy metals


The central metal ion Mn+ (pale
green) can be Ca2+, Mg2+, Fe2+, Fe3+,
and so on. The ligand is EDTA4-,
and the
net charge on the complex is +n-4.
Structural diagrams and ball-andstick models are shown for the two
optical isomers of an [MEDTA]n-4
complex.

Petucci FIGURE 24-24

The porphyrin structure

Structure of
Chlorophyll-A
Hemoglobin carries
O2 through the Febonded to the heme.

29

Make sure to review also the following


concepts covered prior to 2nd exam:
Acids and Bases (e.g. pH, buffers)
Setting up of ICE Table for Aqueous
Equilibria and pertinent calculations and
approximations
Common Ion Effect on Aqueous Equilibria

30