- . . .

I[ [

c. Linkage isomers. In these isomers, the ligands are linked to the €:entral atom through
different atoms. II

Ex. The -N02 ligand can b~ linked to the cen~r~1atomthro.u~h either th.e N ~tom or 0 atom. ~t
is called nitro- when linked through N; It IS called rutrtto- when 11n1ketl
through 0 and IS
written as ONO-. I

129
Learning Modules in General ChemistrY 2

- Chiloter 7 C001J~
d. Coordination isomers. This type of isomer have at least two centers o~ coordination and
I
ConuxlUJll!i .

are formed through exchange of ligands between the coordination feolters (a a cationic
complex and an anionic complex). I

Stereoisomers I I
, These are compounds with the same type and number of atoms and the same chemical bonds
but different spatial arrangements. They cannot be interconverted without breakinglabond.

. a. Geometricisomers. They can beas- or trsns-. The cis- isolrl has two identical
. ligands, adjacent to each other, while the trims- isomer has two Iiga1ndsopposite each
other In the structural formula. They have different properties. i
b. Optical Isomers. ~ese are nonsuperimposable mirror images of eac, other. ,

BONDING IN COORDINATION COMPOUNDS

Valence Bond Th~ry (Localized Electron Model) I

This theory describes bonding in coordination compounds using hybrid iorpitals and electron
pairs. ' I' . "
Although the VSEPRmodel cannot be used for complex ions, it would JII ee safe to assume
that a complex with coordination number of 2 ligands is linear while that with coorc!linationnumber of
6 is octahedral. However, complexes with coordination number 4 can be either e~rahedralor squaref'

~ana~ . , . . ,

Recall that in the Valence Bond Theory, a bond is formed by the overlap' ~f two orbitals and
the subsequent sharing of a pair of electrons between the two atoms in the regiop of overlap. Since
ligands do not usually possess unpaired electrons, the bonding in a complex must result from the .
overlap of ligand orbitals containing a pair of electrons, with vacant orbitals on the I metal ton, thereby
leading to the formation a coordinate covalent bond. II

II I
Octahedral Complexes

Consider the formation of the complex [Cr(H20)6]3+. I

In the ground stfte, the electronic
structure of the free Cr atom is given by

.L L L L L L _J
3d 3d 3d 3d 3d 4s 4~ 4p 4p

The central atom in the complex is Cr3+ which is formed when Cr atom loses 3 frons.

L 1:.. L -!
3d 3d 3d 3d 3d 45
4p ~ i P
4p

Learning Modules In General Cherntstty 2 130

- Chapter 7

Since there are six ligands In the complex, it means that six vacant orbitals
cootltlon

tf
the metal ion are
~ompounds

involved in the formation of coordinate covalent bonds. The six orbitals must cpnie from two vacant
3d orbitals, one vacant 4s orbital and three vacant 4p orbitals. When two d (!)r~itals,one s orbital
and three p orbitals are involved in hybridization., d2sp3 hybrid orbitals are fOrl1hetl. In the Cr atom,
vacant d orbitals in the third main energy level rather than the .fourth main energyI level are involved
because they have lower energy and therefore form stronger bonds. The. hybrids are designated as
I
d2sp3rather than sp3d~ to signifY that the d orbitals come from the energy level beneath the one that
supplies the sand p orbltals.:The complex is sometimes referred to as inner orlJJit~1 complex because
the 3d orbitals are involved rather than the 4d orbitals. I1
The electronic structure of Cr+ in the complex is therefore given by
I
L
3d
L
3d
L
3d d2sp3 1-
Let us consider this time the formation of the complex [FeF6]3-. The eleJronic' structure of the
Fe atom in the ground state is given by .. I··
Feo:[Ar] 3d64s2 t..J..
3d
L
3d
L
3d
L
3d .
L
3d
t J,.
4s 4p
I 4d
4p . 4p 4d
. . I
Fe loses 3 electrons to form Fe3+and the electron,distribution of Fe +is given by3

Fe3+:[Ar]3d54so L L L L L -"
3d 3d 3d 3d 3d 4s ·4p 4p p 4d 4d

Since Fe3+ needs six vacant orbitals to accommodate the electron pairs fr~m the six ligands,
one 4s, two 4p and two 4d orbitals combine to form sp3d2 hybrid orbitals. The electronic structure of
Fe3+in the complex is therefore given by . I
• Fe3+ in [FeF6]3- L L 'L L 'L -
3d 3.d 3d 3d 3d
~
'.
We can see from the above examples that both inner and outer 0 bital complexes are
possible,

When it is possible for both inner orbital and outer orbital complexes to bel formed, how do we
determine which type of orbital bonding will occur?

1. When 3d orbitals are used to form hybrid orbitals, stronger metal-lig~nd bonds are formed
than when 4d orbitals are used. This favors the pairing of electrons and the formation of inner orbital
complexes. II
2. The pairing of electrons required to produce the necessary vacant 139 orbitals for inner
bonding uses energy due to repulsion that would exist between electrons which ar forced to occupy
the same orbital. Since pairing does not have to occur if 4d. orbitals are used to form the hybrids/
this favors the formation of outer orbitals complexes.

131
 I 1

coordi~na6onCompounds
Chapter 7 I I '

Consequently: . I '
When the energy released during bond formation using hybrld orbitals iS much greater than I
the pairing energy, an inner orbital complex is formed. .~ I <'

,~ When the energy released during bond formation Is much lower than the priring energy, an
outer orbital complex is formed. . .' ~

In general, most ligands, except H20 and F, tend to give inner orbital complexes with first
row transition elaments with d4 or d6 configurations. . II

When the configuration of the metal Ion is 3d8, electron pairing is difficult to establish and the
tendency is to form outer orbital complexes. If I
Other Geometries

How do we explain the formation of the square planar complex ion, [~I(~N)'12-, which is
diamagnetic?

The electronic structure of the Ni atom is given by:

t'!" t'!" t'!" 1.. 1.. t,!..

3d 3d 3d 3d 3d 4s 4p 4p 4P
In the complex, the electronic structure of the Ni2+ion is ,

t'!" t'!" ,t'!" t,!..

3d 3d 3d 3d ( )

Another possible structure is the tetrahedral complex like [C.oCI4]~-where t~e distribution of
the central atom C02+ (25 electrons) is II

[IT] [IT] !IJ !IJ' [LJ 0 D D r-l

C02+in [CoCI..]2-
3d 3d 3d 3d 3d . ( Sp3 ) 11
~ I
Crystal Field Theory ,

. This theory explains bonding in complexes in terms of electrostatic forle~. There are two
types of electrostatic interaction in a complex: " I J '
1. The electrostatic attraction between the positive metal ion and the neLa rive ligand or the'
partial negative end of a polar ligand which binds the ligand to the metal. I , ,r
, ., .2. The electrostatic repulsion between the lone pairs on the ligands and th!e ~Iectrons in the d
orbitals of the metal. . .. .' I

Learning Modules 10 General Chemistry 2 132

 I I
!=h~~r 7. . .. . '. Coc:>rdlnrti~ Compounds .

The maqnitude of repulsion is dependent on orientation of the d orbitals in~pl~ed. As a result

of the -metal-ligand interactions, the five d orbitals in an octahedral or tetrahedral] c~mplex are split
between two energy levels. The energy difference between the 2 sets of d orbih1ls is called the
crystal field splitting (4). The magnitude of !1 depends on the metal and the natiure of the ligands
and has a direct effect on the color and magnetic properties of the complexlon. . i I
.' .. I
Octahedral Complexes I I
The ligands in an octahedral complex are oriented along the three axes -it x1 y and z. This
means that of the five d orbitals, the electrons in the dx2_y2 and the dz2 will experi e~ce the greatest
repulsion because they are oriented directly towards the ligands. As a result, the ~ ,rbitals are split
into two energy levels - eg (dx2_y2 and dz2) which has higher energy due to greater repulsion and t2g
(dxy, dyzand dxz)which has lower e~ergy. As. previously men~ioned,the magnit~del·allf!1 depends on
the metal and the nature of the ligand. From the absorption spectra of vano~s complexes, the
ligands can be arranged according to their ability to produce large A in a spectTOcferlcal series.

The Spectrochemical Series

. Let us consid~r the forma~ion.of the. complex [FeF6]3-. The central metal i01 ill this complex is
Fe3+ and the electronic structure IS qrven by .

Fe3+: [Ar]3d6 4so L

3d
L
3d
L
_3d
L
3d
L
3d
_ _. _ -
4s 4p 4p
-
4p 4d
J - .- -
4d ~4f 4d 4d

Since r is a ligand with low A (weak field), the electrons will remain unp~ir~d in the five 3d
orbitals. The 4d orbitals will be used in hybridization and the complex will use SR3df hybrid orbitals
for bonding. The electronic structure 'of the complex is the same as that predicted u,Ing the Valence
, bond Theory. " I '. .
Fe3+ in [FeF6]3-
.
L
3d
iii
3d 3d 3d 3d
L
(
_
sp'd'
-
) 111 - 4d 4d
-
. If instead of F, the ligand is CW which is a strong field ligand (high A), tht energy of the 3d
orbitals (which contain electrons and will therefore exhibit repulsion towards th~ 19ne pairs of the
ligands) will be split with electrons filling up the orbitals with lower energy (t29) and the eg orbitals
being involved in the formation of d2sp3 hybrid orbitals: The electronic structure ~f ,!he complex will
now be I
i.i t.i L - 4d- 4d-
-) 4d -
4d 4d
~
3d 3d 3d (

If we compare the electronic structure of the two complexes mentioned

Learning Modules in Gen.~1Q1:kiemi.L.!·lil.isi!.,tlYl-J::...2 __""-l- _ 133

Chapter 7

i i
r t
t
* !:J.(low)

Tetrahedral Complexes

.: In this geometry, the ligands are oriented between the axes and the, d orbitals which
experience the greatest repulsion is the t2g group. When a high field ligand forms t e complex, the
energies are split as follows: '
I
I , 1
l
!:J.(high)

--------- , '

1
d orbitals in 'a free metal ion

Square Planar Complexes

In this geometry, the ligands are oriented towards the corners of a square. Consequently,
when a high field ligand is involved the energy of the d orbttals are split as follows: !

22
dx--y I
I
I
-- -- -- --

d orbitals in a free metal ion d orbitals when !:J.is high

Exercise:

Compare the magnetic properties of [Ni(CN)4!- and [NiClj-.

" Leamlng Modules In General Chemistry 2 I 134

 . I I

I I ..
Chapter 7 coordin~tion Compounds

Paramagnetismand Color I
I
Complexes where the metal ions possess a number of unpaired electrons are said to be
paramagnetic. The presence of unpaired electrons may lead to the formation of cJlo~edcomplexes.

The color of a complex is generallydependent on the nature of the metal, its oxidation state
and the nature of the ligands. A complex exhibits color if the transition-metal ion has a partially filled
r
d orbital. Fe3+ in [Fe(H20)s]3+ has 5 electrons in the 3d sublevel and is therefor dolored. Ions with
completely empty (e.q, ca2+) or completely filled. d sublevels (e.g. Cd2+) are uSp'allYcolorless. A
compound is colored if it absorbs visible light which consists of electromag~e~ic radiation with
wavelengths that range from 400 nm to 700 nm. The energy of the electrorn.agnetic radiation is
inversely proportional to its wavelength. . . . I[ I .
. . E = hv = hc fA. . .
A compound absorbs the visible radiation that has the energy to bring tHe 11ectronfrom the
. ground or lowest energy state to the excited state. Hence, the color of a sUbstanfe!is determined by
the quantity of energy that it absorbs. ~.

When a substance absorbs visible radiation, the color observed correspords to the remaining
colors that are transmitted or reflected by the object.

Description of Artist's Color Wheel

Wavelength Range of Color Absorbed Color Observed
Absorbed Radiation (nm)
II I
400 _ 430' Violet Yellow'
430 - 490· Blue Orange I
490 _ 560 Green Red
560 _ 580 Yellow Violet II
580 - 650 Orange Blue I·
650 -750 . Red Green

When an 'electron can be excited from a d orbital of lower energy to al orbital of higher di
energy, color formation may result. The observed color depends on the energy needed to promote
the' electron to the higher-energy d orbital. This energy depends on the vallulof Ll· when the
degeneracy of the d orbitals is split according to the ligands in the complex. For ~hit the reason, the
[Fe{CN)6]3- complex is colored yellow because the high Ll value (page 134) Inecessitates the
absorption of elarqe amount of energy to promote electrons in the tZg dorbitals to Ithe eg dorbitals.
This corresponds to a low wavelength o! absorbed. radiation tha~ falls within t~e ~OO nm-430 nm
range. On the other hand, the [FeFs]3 complex IS colorless since the Ll value IS so small, the
resultlr:'gwavelength is so large that it does not fall within the visible region. . I
. ~ I
. Exercise: I
Compare the magnetic properties of the [coa.r and [Co(NHJ)./' comp'fe~.

I
Leprojog Mqdules in General ChemjstrY 2 135