CHAPTER THREE

COORDINATION CHEMISTRY OF TRANSITION

METALS
• Coordination chemistry concerns compounds in which a small number
of molecules or ions called ligands surround a central metal atom or
ion.
• Each ligand (from the Latin ligare, meaning “to bind”) shares a pair of
its electrons with the metal.
• The metal ligand bond, often represented as M :L, is an example of a
coordinate-covalent bond in which both the electrons come from one
atom.
• Transition metal ions characteristically form coordination compounds,
which are usually colored and often paramagnetic.
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• A coordination compound typically consists of a complex ion, a
transition metal ion with its attached ligands, and counterions, anions or
cations as needed to produce a compound with no net charge.
Example: [Co(NH3)5Cl]Cl2 is a typical coordination compound.
• Coordination compounds have two types of valency: the primary valency
the oxidation state and the secondary valency the coordination number.
• Each ligand functions as a Lewis base and so donates a pair of electrons
to form the ligand–metal bond. Thus, every ligand has at least one
unshared pair of valence electrons. In forming a complex, the ligands are
said to coordinate to the metal.

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• A ligand is a neutral molecule or ion having a lone electron pair that can
be used to form a bond to a metal ion.
• The formation of a metal–ligand bond therefore can be described as the
interaction between a Lewis base (the ligand) and a Lewis acid (the
metal ion).
• The resulting bond is often called a coordinate covalent bond.
• A ligand that can form one bond to a metal ion is called a monodentate
ligand or a unidentate ligand (from root words meaning “one tooth”).
• Some ligands have more than one atom with a lone electron pair that can
be used to bond to a metal ion. Such ligands are said to be chelating
ligands, or chelates. A ligand that can form two bonds to a metal ion is
called a bidentate ligand.
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Types of ligands based on coordination number:
1. Monodentate ligands: The word monodentate comes from the Greek monos and
the Latin dentis and, means “one tooth.”

 A monodentate ligands shares only a single pair of electrons with a metal atom or
ion (these ligands have one donor atom that can form a single coordinate bond with
the metal ion).

Examples: H2O, NH3, x- (x = F, Cl, Br, I), CN-, SCN-, OH-, …

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2. Bidentate ligands: These ligands have two donor atoms that can simultaneously
coordinate with the metal ion, forming two coordinate bonds.

Examples: Ethylenediamine (en), oxalate ion (C2O42-)

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3. Polydentate ligands: These ligands have more than two donor atoms that can form
multiple bonds with metal ion.

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Types of ligands based on charge:
1) Neutral ligands: These ligands don’t carry a charge.
Examples H2O, NH3, CO, NO, H2NCH2CH2 (en), CH3NH2, py, bpy,
2) Anionic ligands: These ligands carry a negative charge.
Examples: CN-, OH-, C2O42-, SO42-, x- (x = F, Cl, Br, I), O2-, S2O32-, NO2-,SCN-, etc.
Types of ligands based on functionality:
1) Chelating ligands: These ligands can form a ring structure by bonding to a central
metal ion through multiple donor atoms. Bidentate and polydentate ligands are all
examples of chelating ligands.
2) Ambidentate ligands: These ligands can bind to the metal through two different
atoms, but only one binds at a time.
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 Ambident ligands are monodendate ligands which binds with the metal ion through more
than one site.

 If we represent this type of ligand as :AB:, then it can form one of two possible coordinate-
covalent bonds, either

M :AB: or :AB: M, with a metal atom.

 Common ambidentate ligands include cyanide (CN-), thiocyanate (SCN-), and nitrite (NO2-).

 Bridging ligands: those containing two pairs of electrons shared with two metal atoms
simultaneously. The interaction of such ligands with metal atoms can be represented as

M : L: M.

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• Ligands of the bridging type include amide (NH2-), carbonyl (CO), chloride
(Cl-), cyanide (CN-), hydroxide (OH-), nitrite (NO2-), oxide (O2-), peroxide
(O22-), sulfate (SO42-) and thiocyanate (SCN-).
• Coordination number: the total number of coordinate bonds formed between
a central metal ion and its ligands.
• Inner coordination sphere or the first sphere refers to ligands that are directly
bound to the central metal.
• Outer coordination sphere or the second sphere refers to other ions that are
attached to the complex ion.
• In [Pt(NH3)6]Cl4, NH3 is the inner sphere ligand, Cl is the outer sphere ligand.
Charge of a complex
• In the formula of the complex ion: square brackets group together the species
making up the complex ion.

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• The overall charge is shown outside the brackets.
• The overall charge is the sum of the individual charges of the transition
metal ion and those of the ligands present in the complex.
Worked examples
1. State the formula and charge of the complex ion made from one
titanium(III) ion and six water molecules. [Ti(H2O)6]3+
• The formula shows that six H2O ligands are bonded to one titanium(III)
ion.
• As water is a neutral ligand, the overall charge on the ion is the same as
the transition metal ion, which is +3.

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2. What is the oxidation number of the transition metal in the complex ion
[Co(H2O)5Cl]+?
 This complex ion has five neutral water ligands with no charge, and one
chloride ligand with a charge of –1.
 Overall the complex ion has a 1+ positive charge.
 In [Co(H2O)5Cl]+, cobalt must have the oxidation state +2 to give the
overall charge of +1.

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Nomenclature of Coordination compounds
 The IUPAC publication nomenclature of inorganic chemistry, contains the rules for
the systematic naming of coordination compounds.
 The basic rules are summarized as follows:
1. The positive ion is named first followed by the negative ion. Example; K2[PtCl4],
potassium tetrachloroplatinate(II)
2. When writing the name of a complex, the ligands are quoted in alphabetical order,
regardless of their charge (followed by the metal).
3. When writing the formula of complexes, the complex ion should be enclosed by
square brackets. The metal is named first, then the coordinated groups are listed in
the order: negative ligands, neutral ligands, positive ligands (and alphabetically
according to the first symbol within each group). The names of negative ligands end
in – o, and neutral groups have no special endings. Ligands that act as anions which
end in “-ide” or “-e” are replaced with an ending “-o” (e.g., chloride → chloro).
Anions ending with “-ite” and “-ate” are replaced with endings “-ito” and “-ato”
respectively (e.g. Nitrite → Nitrito, Nitrate → Nitrato).

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 Ion Ligand name
Cl- chloride chloro
F- fluoride fluoro
Br- bromide bromo
I- iodide iodo
OH- hydroxide hydroxo
SO42- sulfate sulfato
O2- oxide oxo
OH- hydroxide hydroxo
CN- cyanide cyano
SCN- thiocyanate thiocyanato
S2O32- thiosulfate thiosulfato
C5H7O2- acetylacetonate acetylacetonato

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Most neutral molecules that are ligands carry their normal name. The few exceptions
are the first four on the chart: ammine, aqua, carbonyl, and nitrosyl.
Molecule name Ligand name
NH3 ammonia ammine
H2O water aqua
CO carbon monoxide carbonyl
NO nitric oxide nitrosil
4. Where there are several ligands of the same kind, we normally use the prefixes di, tri,
tetra, penta, and hexa etc… to show the number of ligands of that type. An exception
occurs when the name of the ligand includes a number, e.g. Dipyridyl or
ethylenediamine. To avoid confusion in such cases, bis, tris, and tetrakis, etc… are
used instead of di, tri, and tetra and the name of the ligand is placed in brackets.
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5. The oxidation state of the central metal is shown by a Roman numeral in brackets
immediately following its name (i.e. no space, e.g. titanium(III)).
6. Complex positive ions and neutral molecules have no special ending but complex
negative ions end in “-ate”.
 For example, chromium becomes chromate, manganese becomes manganate, and
molybdenum becomes molybdenate, etc. Note that the –ate tends to replace –um
or –ium, if present.
 Some metals, such as copper, iron, gold, silver, tin, lead, … retain the latin stem
for the metal and become cuprate, ferrate, aurate, argentate, stannate, plumbate,
respectively, in an anionic setting.
7. If the complex contains two or more metal atoms, it is termed polynuclear. The
bridging ligands which link the two metal atoms together are indicated by the
prefix,µ -. If there are two or more bridging groups of the same kind, this is indicated
by µ-di, µ-tri etc…
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 There are two ways to handle ambidentate ligands.
 One is to use a slightly different form of the name, depending on the
atom that is donating the electron pair to the metal.
 The second is to put the symbol of the donating atom before the name of
the ligand.
• SCN- might be called thiocyanato or S-thiocyanato, whereas NCS- would
be isothiocyanato or N-thiocyanato.
• NO2- might be called N-nitrito or nitro; whereas ONO- referred to as O-
nitrito or nitrito
• CN- is called cyano; NC- is isocyano

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Examples
Example 1: [Pt(NH3)4]Cl2
 There are two negative chloride ions outside of the complex, so the complex itself
must have the formula [Pt(NH3)4]2+.
 The ammonia ligands are neutral; thus, the platinum must have an oxidation state of
+2. As a result, we start with the stem name platinum(II).
 The ligand is ammonia, which has the name ammine.
 But there are four ammonia ligands, so the prefix is added to give tetraammine.
 Finally, the chloride anions must be included.
 They are free, uncoordinated chloride ions, so they are called chloride, not chloro.
 We do not identify the number of chloride ions because the oxidation state of the
metal ion enables us to deduce it.
 Hence, the full name is tetraammineplatinum(II) chloride.

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Example 2: [PtCl2(NH3)2]
 This is a non-ionic species, so it will have a one word name.
 Again, to balance the two chloride ions, the platinum is in the +2 oxidation state, so
we start with platinum(II).
 The ligands are named ammine for ammonia and chloro for chloride.
 Alphabetically, ammine comes before chloro; thus, we have the prefix
diamminedichloro.
 The whole name is diamminedichloroplatinum(II).
Example 3: K2[PtCl4]
 Again, two words are needed , but in this case, the platinum is in the anion, [PtCl4]2-.
 The metal is in the +2 oxidation state, so the anionic name will be platinate(II) .
 There are four chloride ligands, giving the prefix tetrachloro and the separate
potassium cations.
 The complete name is potassium tetrachloroplatinate(II).
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Example 4: [Co(en)3]Cl3
 The complex ion is [Co(en)3]3+.
 Because (en), H2NCH2CH2NH2, is a neutral ligand, the cobalt must be in
a +3 oxidation state.
 The metal, then, will be cobalt(III).
 The full name of the ligand is ethylenediamine and contains a numerical
prefix, so we use the alternate prefix set to give tris(ethylenediamine)
parentheses are used to separate the ligand name from the other parts of
the name.
 Finally, we add the chloride anions.
 The full name is tris(ethylenediamine)cobalt(III) chloride.

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Example 5: [Co(NH3)4Cl2]Cl.
 We start by naming the complex cation.
 The ligands are named alphabetically with ammine first and then chloro.
 There are four ammonias and two chlorides, so the prefixes tetra- and di- are used.
 The cobalt oxidation state is determined by tracing the charges back as follows:
 The net charge on the complex cation must be 1+ to balance the one 1- chloride anion.
 Since there are two chlorides in the coordination sphere, the cobalt must be 3+ in order for
the net charge on the cation to come out as 1+.
 Accordingly, the full name of the compound is tetraamminedichlorocobalt(III) chloride

Example 6: (NH4)2[Pt(NCS)6]
 Here we have a platinum-containing complex anion and the common ammonium ion, NH4+,
as the cation.
 Given that the ligand is written with the N symbol first, we know that it is the isothiocyanato
(or, alternatively, N-thiocyanato) form of the ambidentate ligand.
 There are six of these ligands, so we use the hexa- prefix.
 The anion must have a net charge of 2- to balance the two 1+ ammonium cations.
 Since the thiocyanate ion is also 1-, the platinum oxidation state must be 4+ to give a net 2-
charge on the anion.
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 Because the platinum is contained in a complex anion, its-um suffix is removed and replaced
with -ate.
 Accordingly, the full name of the compound is ammonium hexaisothiocyanatoplatinate(IV).

Example 7: Write the formula for the compound (acetylacetonato)tetraaquacobalt(II) chloride.

 The acac and four waters constitute the coordination sphere that with the cobalt(II) cation are
set apart in brackets.
 The net charge on the complex cation is 1+ (because the acac is 1-), so one chloride
counteranion is needed.
 The formula of the compound is [Co(acac)(H2O)4]Cl .
Exercise: Write the formula for the following coordination compounds:
(a) diamminetetraaquachromium(II) ion
(b) Potassium hexacyanoferrate(III)

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Isomerism
 Compounds that have the same chemical formula but different structural
arrangements are called isomers.
 Isomers can be discussed under two general categories:
• Structural Isomerism: occurs between ligands can be attached to the metal in
different ways (different bonds) or where the isomers contain the same atoms but one
or more bonds differ. It can be classified into five different types.
– Ionization isomers
– Hydration isomers
– Linkage isomers
– Coordination isomers
– Polymerization isomers
• Stereoisomerism: where all the bonds in the isomers are the same but the spatial
arrangements of the atoms are different.
– Geometrical isomerism
– Optical isomerism
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• Ionization isomers: This type of isomer is due to the exchange of groups between
the complex ion and the ions outside it.

Example: [CoBr(NH3)5]SO4 and [Co(SO4)(NH3)5]Br

• Hydration Isomers: This is very closely related to ionization isomer but the
difference is in hydrate isomers, the exchange is between a water molecule and
another ligand in the coordination sphere. Example; CrCl3.6H2O may be any of the
three compounds.

[Cr(H2O)6]Cl3 - violet in color

[CrCl(H2O)5]Cl2.H2O – light green

[CrCl2(H2O)4]Cl.2H2O – dark green

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• Linkage isomers: it is different in the identity of the atom that a given ligand uses to
attach to the ion. A ligand may have more than one atom with a lone pair that can
bonded to the metal ion but because of its size or shape, only one atom can bond to
the metal ion at a time.
[Co(ONO)(NH3)5]Cl2 and [Co(NO2)(NH3)5]Cl2
• Coordination isomers: when both positive and negative ions are complex the
isomerism may caused by the interchange of coordination groups from one sphere to
another.
[Co(NH3)6] [Cr(CN)6] and [Cr(NH3)6][Co(CN)6]
• Polymerization isomers: This is not truly isomerism, since it occurs in the empirical
formula of compounds, their molecular weights being different.
[Pt(NH3)2Cl2] and [Pt(NH3)4][PtCl4] 26
Stereoisomers
 Stereoisomers have the same molecular formula and the same atom connectivity, but
differ in the spatial arrangement of different atoms or groups about a central atom
 It can also be divided into two:
– Geometrical isomerism
– Optical isomerism
a) Geometrical isomerism: These complex compounds have the same ligands in the
coordination sphere but the relative position of the ligands around the central metal
atom is different.
 Geometric isomers must have two different ligands, A and B, attached to the same
metal, M.
 The term cis is used for the isomer in which ligands of one kind are neighbors, and
trans is used to identify the isomer in which ligands of one kind are opposite each
other.
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 For square planar compounds, geometric isomerism occurs in compounds of the form
MA2B2, such as [PtCl2(NH3)2].

 Geometric isomers also exist for square planar complexes of the form MA2BC.
 There are two formulas of octahedral compounds having only two kinds of ligands
for which geometric isomers are possible.

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 Compounds with the formula MA4B2 can have the two B ligands on opposite sides or as
neighbors. Hence, these are known as trans and cis isomers.

 Cis–trans isomerism in [CoCl2(NH3)4]+

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 Octahedral compounds with the formula MA3B3 also can have geometric isomers.
 MA3B3 type complexes may have two isomeric forms called fac- and mer-(facial and
meridional). Fac isomers have three identical ligands on one triangular face; mer
isomers have three identical ligands in a plane bisecting the molecule. Similar
isomers are possible with some chelating ligands.
 Example [CoCl3(NH3)3]

 A number of examples of these types have been isolated and characterized and they
show very different chemical and biological properties.
 Thus for example, cis-PtCl2(NH3)2 is an anti-cancer agent (cis-platin) whereas the
trans-isomer is inactive against cancer (it is toxic), and so not useful in
chemotherapy.
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Optical Isomerism: A pair of enantiomers consists of two molecular species which are non-
superimposable mirror images of each other.
 When the solution of certain complex compounds are placed in the path of a plane polarized
light, they rotate its plane through a certain angle which may be either to the left or to the
right. This property of a complex of rotating the plane of polarized light is called its optical
activity and the complex possessing this property is said to be optically active.
 Optically active complexes are said to exist in the following forms:
(1) One which rotates the plane of polarized light towards right (in clockwise direction) is said
to be dextro-rotatory or d-form. d-form is also represented by placing (+) sign before its name
or formula.
(2) One which rotates the plane of polarized light towards left (anti-clockwise direction) is
called laevo-rotatory of l-form. l-form is also represented by putting (-) sign before its name or
formula.
 The optical (d- and l-) isomers have basically the same properties (melting points, boiling
points, etc.) although they differ in their action on polarized light.
 The d- and l- forms are mirror images to each other just as left hand is the mirror image of
the right hand.
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 The most necessary and sufficient condition for a molecule to show optical
isomerism (to exist in d- and l- forms) is that the molecule should be asymmetric (it
should have no plane of symmetry) and should not be superimposable on its mirror
image.

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 Optical isomerism can be seen in the structures of the two isomers of [Ni(en)3]2+.

Optical isomers of [Ni(NH2CH2CH2NH2)3]2+

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 Bonding in Transition Metal Complexes
 Bonding in Coordination Compounds: Theories of bonding should explain three
important properties of transition metal complexes: Structure, magnetic property, and
color.
 Theories of bonding are: (i) Valence bond theory, (ii) Crystal Field Theory (iii)
Molecular orbital theory
(i)Valence Bond theory: In terms of valence bond theory, the filled orbital of the ligand
overlaps with an empty orbital of the metal ion, therefore, giving rise to a coordinate
covalent bond.
 The Valance Bond model proposes that the geometry of the complex ion depends on
the hybridization of the metal ion.

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 • Table 1: review hybrid orbital of the central atom

Hybrid orbitals Atomic orbitals Number of Electron-pair

used hybrid orbitals geometry • The theory considers which
sp s+p 2 Linear atomic orbitals on the metal
sp2 s+p+p 3 Trigonal planar
sp3 s+p+p+p 4 Tetrahedral
are used for bonding. From
dsp2 s+p+p+ d 4 Square planar this the shape and stability of
sp3d or dsp3 s+p+p+ p+d 5 Trigonal bipyramidal
the complex are predicted.
sp3d2 or d2sp3 s+p+p+ p+d+d 6 Octahedral

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 The formation of a complex may be considered as a series of hypothetical steps. First
the appropriate metal ion is taken, e.g. Co3+. A Co atom has outer electronic structure
3d74s2. Thus a Co3+ ion will have the structure 3d6, and the electrons will be
arranged:

 If this ion forms a complex with six ligands, then six empty atomic orbitals are
required on the metal ion to receive the coordinated lone pairs of electrons.
 The orbitals used are the 4s, three 4p and two 4d. These are hybridized to give a set
of six equivalent sp3d2 hybrid orbitals.
 A ligand orbital containing a lone pair of electrons forms a coordinate bond by
overlapping with an empty hybrid orbital on the metal ion. In this way bond is
formed with each ligand.

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 Since the outer 4d orbitals are used for bonding this is called an outer orbital complex.
The energy of these orbitals is quite high, so that the compiex will be reactive or
labile.
 The magnetic moment depends on the number of unpaired electrons. The 3d level
contains the maximum number of unpaired electrons for a d6 arrangement, so this is
sometimes called a high-spin or a spin-free complex.
 An alternative octahedral arrangement is possible when the electrons on the metal ion
are rearranged as shown below.
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 Since low energy inner d orbitals are used this is called an inner orbital complex.
Such complexes are more stable than the outer orbital complexes. The unpaired
electrons in the metal ion have been forced to pair up, and so this is now a low-spin
complex. In this particular case all the electrons are paired, so the complex will be
diamagnetic.
 The metal ion could also form four-coordinate complexes, and two different
arrangements are possible.

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 Examples about the formation of covalent bond according to valance bond model

• Hybrid orbitals and bonding in the octahedral

• Hybrid orbitals and bonding in the
[Cr(NH3)6]3+ ion.
square planar [Ni(CN)4]2- ion.
• Cr = [Ar]4s13d5 , therefore Cr(III) is a d3 case
• Ni = [Ar]4s23d8 Ni(II) is a d8 case

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 Hybrid orbitals and bonding in the tetrahedral [Zn(OH)4]2- ion

40
 For octahedral Fe(III) complexes, we must account for the existence of both high-
and low-spin complexes. Fe3+ ion has:

3d 4s 4p
 For a low-spin octahedral complexes such as [Fe(CN)6]3-; the diagram becomes:

3d d2sp3
 For a high-spin octahedral complex such as [FeF6]3-; the diagram becomes:

3d sp3d2
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 VBT rationalizes the geometry and magnetic property of complex ions
but it does not explain the color of the metal complexes.

 It fails to predict whether a 4-coordinate complex will be tetrahedral or

square-planar and whether an octahedral complex will be low-spin or
high-spin.

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(ii) Crystal Field Theory:
 Crystal field theory differs from valence bond theory in viewing the complex as held
together by purely electrostatic.
 Ligands are considered as point charges and there are no metal–ligand covalent
interactions.
 Consider an octahedral geometry; an octahedral complex is constructed by placing
six ligands along the x, y, and z axes.
 In order to understand clearly the interactions that are responsible for crystal or ligand
field effects in transition metal complexes, it is necessary to have a firm grasp of the
geometrical relationships of the d orbitals.

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 • When a complex is formed,
electrons in the d-orbitals will
feel an electrostatic repulsion and
their energies will be raised.

 An electron in a dx2-y2 or dz2 orbital will be repelled more than an electron in one of
the dxy, dxz, dyz orbitals. Recall that the dx2-y2 or dz2 are pointing directly towards the
ligands, while dxy, dxz, dyz are pointing between the ligands at an angle of 45°.
 The energies of the dx2-y2 and dz2 are raised more than the energies of the dxy, dxz, dyz
orbitals.
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 The effect of the ligand is to split the d-subshell into two sets of energy levels, t2g and eg. The diagram
below shows the splitting of d-orbitals in an octahedral complex.

45
 The d orbitals split into two groups. The difference in energy between these groups is
called the crystal field splitting energy, Δo.

The figure above shows the splitting of the d orbitals in an octahedral crystal field, with the energy
changes measured with respect to the barycentre, the energy level shown by the dashed line.
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 The magnitude of the crystal field splitting, ∆o, depends on the following factors.
(i) Nature of ligand: Studies have shown that keeping the same central metal atom, on
varying the ligands attached to it, the magnitude of Δo is different in each case.
 Ligands which cause only a small degree of splitting are termed weak field ligands
and those which cause a large splitting are called strong field ligands.
 The common ligands are arranged in order of their strength and the series is called the
spectrochemical series.

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  CO and CN- are called strong field ligands, because they cause a large splitting of the
d-orbital energy levels. The halide ions and hydroxide ions are weak field ligands,
because they split the d-orbitals to a lesser extent.
 The effect of ligands and splitting energy on orbital occupancy

Strong field ligands lead to a larger splitting energy

Weak field ligands lead to smaller splitting energy

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(ii) Charge on the metal atom: The magnitude of Δo increases as the charge on central
metal atom increases.
The table below shows crystal field splittings for hexa-aqua complexes of M2+ and M3+

• For first row transition metal ions, the values of Δo for M3+ complexes are roughly
50% larger than the values for M2+ complexes.
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(iii) Position of the metal in the transition series: The magnitude of Δo increases down
the group of transition elements.

The table below shows Δo crystal field splittings in one group

 The value of Δo also increases by about 30% between adjacent members down a
group of transition elements

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 Crystal field stabilization energy (CFSE): The crystal field stabilization energy
(CFSE) is the energy by which the complex is stabilized relative to the free metal
atom where there is no splitting of d orbitals.

 It can be calculated by: CFSE = {(neg x 3/5) – (nt2g x 2/5)} Δo where neg = number of
electrons in eg orbitals and nt2g = number of electrons in t2g orbitals.

 Consider the case of d10 ion where under the influence of an octahedral ligand field
four electrons will move to higher energy eg orbitals and six electrons to lower energy
t2g orbitals. Thus, the result for d10 system (e.g. Zn2+) is no change in energy.

CFSE = {(4 x 3/5) – (6 x 2/5)}Δ0 = 0

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 A similar result would be obtained for a d0 (e.g. Sc3+) and a d5 (e.g. Mn2+, Fe3+)
electron configuration. In other words such ions would not be affected by the field of
the ligands.

 Let us consider the other cases. Taking for example [Ti(H2O)6]3+ in which metal ion
has d1 configuration the CFSE is -0.4Δo. Similarly for d2 configuration (as in
[V(H2O)6]3+) the CFSE is -0.8Δo and in d3 (Cr3+) and d8 (Ni2+) it will be –1.2Δo.

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• Table: Octahedral crystal field stabilization energies (CFSE) for dn configurations; pairing energy, P, terms are
included where appropriate.

53
 It can be assumed that the electrons added beyond d3 will occupy eg orbitals in
preference to pairing up in t2g orbitals.
 This is reasonable, since there is a pairing energy (P) associated with bringing
electrons close to form a pair in an orbital.
 However, if the interaction between the metal ion and the ligands is sufficiently large
so that Δo > P, it becomes more energetically favorable for the fourth electron added
to occupy t2g orbital. Ligands which produce this effect are known as strong-field
ligands and the complexes they form are called low-spin complexes.
 Whereas ligands for which Δo< P are known as weak field ligands and they form
high-spin complexes. Thus, when calculating the CFSE of a strong field low-spin
complex it is necessary to include the pairing energies associated with the additional
electron pairs.

54
 In such cases CFSE for a low-spin complex (CFSEL) can be written as:
 CFSEL= {(neg x 3/5) – (nt2g x 2/5)}Δo + n(P) where, n(P) = number of additional
electron pairs for a low-spin case
 It is important to note that for a given metal ion the pairing energy (P) is constant.
Thus, when the configuration is d4, two cases arise: high-spin case and low-spin case.
(i) d4 high spin case
This case arises when the ligands attached to the metal are weak field ligands. The
electronic configuration of d-orbitals in this case is t2g3 eg1 and the CFSE will be:
( 3 ×-0.4Δo) + 0.6Δo = -0.6Δo
(ii) d4 low spin case
This case arises when the ligands attached to the metal are strong field ligands. The
electronic configuration of d-orbitals in this case is t2g4 eg0 and the CFSE will be:
(4×-0.4Δo) = -1.6Δo + P
 The two cases differ in the number of unpaired electrons. The CFSE in the second
case is higher than in the first case.

55
 Similar situation can be observed in complexes of metal ions with d5, d6 and d7
configurations

 Pairing energy, P, depends mainly on the electronic distribution of the central metal
ions and its value can be obtained from the atomic spectra of the elements

 The Δo, which depends on metal ion, ligand and the geometry of the complex, is
obtained from the electronic spectra of the complex. Consideration of the data related
to P and Δo for metal ions of d4 to d7 configurations (Table 4) show that when Δo>P,
low-spin complexes are formed and when Δo< P then high-spin complexes are
formed.

56
Figure: The occupation of the 3d orbitals in weak and strong field Fe3+ (d5) complexes.

57
 Tetrahedral Complexes
The tetrahedral crystal field

 The figure below shows a convenient way of relating a tetrahedron to a Cartesian axis
set.
 With the complex in this orientation, none
of the metal d-orbitals points exactly at the
ligands, but the dxy, dyz and dxz orbitals
come nearer to doing so than the dz2 and
dx2-y2 orbitals.
 The consequence is that the dxy, dxz, and
dyz, the t2 set, become higher in energy
than dx2-y2 and dz2, the e set.
58
 For a regular tetrahedron, the splitting of the d-orbitals is inverted compared with that
for a regular octahedral structure, and the energy difference (Δt) is smaller.
 It is easy to show by geometry that the magnitude of Δt < Δo, so as long as ligands of
the same type are used in both cases. 59
 Tetrahedral complexes are always high-spin (small ∆t)
 The magnitude of crystal field splitting in tetrahedral complexes (Δt) is considerably
less than in octahedral complexes.
 Since there are only four ligands, the ligand field is only 2/3 times of the octahedral
field and since the orbitals do not coincide with the direction of the ligands, the
crystal field splitting is further reduced by a factor of 2/3. Therefore the crystal field
splitting in tetrahedral complexes (Δt) is approximately 4/9 of the octahedral field
(Δo).

 The CFSE for d0, high spin d5, and d10 configurations is zero in both octahedral and
tetrahedral cases. In all other cases the octahedral CFSE is greater than that of
tetrahedral CFSE.
 In general octahedral complexes are more stable and more common than tetrahedral
complexes, partly because of the formation of six bonds instead of four and also
because of larger CFSE.
60
 Crystal field stabilization energy for tetrahedral
 CFSE for tetrahedral complexes = {(nt2 x 2/5Δt) – (ne x 3/5 Δt) (where nt2 and ne are
the number of electrons at t2 and e orbitals respectively).

t2

CFSE for [CoCl4]2- = {(3 x 2/5Δt) – (4 x 3/5 Δt) = -1.2 Δt

61
 Transition Metal Complexes and its color
 The origin of the color of complex ions: For most complexes, the crystal field splitting, ∆ is of the
same magnitude as the energy of the visible light. When light strikes the complex, the electron in the
t2g level absorbs the component of light energy of proper frequency and gets raised to the eg level.
 When a component of the visible light is absorbed by the electron, the complex displays the
complement of the color of light that is absorbed.
Complementary colors

62
 For example, [Ti(H2O)6]3+ has a crystal field splitting ∆o, that corresponds to the
energy of light in the yellow-green portion of the spectrum. When white light passes
through a solution of [Ti(H2O)6]3+ complex, yellow light is absorbed and the light
emerges appears violet.

 When the ion absorbs light, electrons can move from the lower t2g energy level to the
higher eg level. The difference in energy between the levels (Δ) determines the
wavelengths of light absorb.
 The color of a coordination compound is determined by the Δ of its complex ion. For
a given ligand, the color depends on the oxidation state of the metal ion and for a
given metal ion, the color depends on the ligand. 63
The Magnetic Properties of Transition Metal Complexes:

 The magnitude of the crystal field splitting also determines the magnetic properties of
a complex ion.

 Magnetic properties are determined by the number of unpaired electrons in the d

orbitals of the metal ion. For example, the [Ti(H2O)6]3+ ion, having only one d
electron, is always paramagnetic.

 However, for an ion with several d electrons, the situation is less clear cut. Consider,
for example, the octahedral complexes [Mn(H2O)6]2+ and [Mn(CN)6]4- is shown
below.

64
 The electron configuration of Mn2+ is [Ar]3d5, and there are two possibility to
distribute the five electrons among the d orbitals depending on the nature of the
ligands.

65
 Crystal field theory can bring together structures, magnetic properties and electronic
properties
 Trends in CFSEs provide some understanding of thermodynamic and kinetic aspects of d-
block metal complexes
 Crystal field theory is surprisingly useful when one considers its simplicity.

Limitations
 Although we can interpret the contrasting magnetic properties of high- and low-spin
octahedral complexes on the basis of the positions of weak- and strong-field ligands in the
spectrochemical series, crystal field theory provides no explanation as to why particular
ligands are placed where they are in the series.

66
 Bonding in Transition Metal Complexes
 Molecular Orbital Theory of Coordination Complexes: Although Crystal Field
theory accounts for many features of complexes including their color it still leaves
some facts unexplained. The color of compounds like KMnO4 (Mn7+ has no d
electrons) cannot be explained.
 One of the important experimental facts is the spectrochemical series where many
anionic ligands turn out to be quite weak field ligands.
 Also quite strangely neutral ligands and very weak or even poor Lewis bases (for
example CO) turn out to be extremely strong field ligands. The above is quite
contrary to the Crystal field theory assumption of an electrostatic interaction between
the metal ion and the ligand.

67
 In contrast to crystal field theory, the molecular orbital model considers covalent
interactions between the metal centre and ligands.

Complexes with no metal-ligand π-bonding

 As an example let us choose the complex [Co(NH3)6]3+.This complex contains NH3

as the ligand which can only participate as a sigma-donor to the metal ion (the
nitrogen atom does not have any low lying orbitals to participate in any additional
type of bonding).

68
 How do we construct the molecular orbital diagram for this complex?

 We can use simple symmetry arguments to come out with a picture that would be
understandable. Let us first consider the metal orbitals. The valence orbitals available
are 3d, 4s, and 4p. So a total of nine orbitals are available. Which of these orbitals are
suitable to be used in sigma-bonding?

 Remember that we are constructing a molecular orbital diagram for an octahedral

complex. This means that the orbitals that we can use should have their lobes pointed
along the axes (in order to have a positive and head-on overlap with the ligand
orbitals).

69
 Obviously the 4s orbital is quite suitable. This is labeled as a1g. All the 4p orbitals are
also suitable (px, py, pz are along the x, y and z directions). These are labeled as t1u.

 Among 3d orbitals only two (the orbitals dx2-y2 and dz2) are suitable since they have
the lobes along the axes. These are labeled eg. however, the orbitals dxz, dyz and dxy are
not suitable since ligand orbitals cannot overlap with them to give a positive overlap.
These cannot be utilized by the metal for sigma-bonding. These remain non-bonding
and are labeled as t2g.

 Thus we conclude, that of the 9 valence orbitals of the metal six are suitable for
forming sigma-bonding (a1g, t1u, eg) and three are non-bonding orbitals (t2g).

70
 Let us assume that by a linear combination of the ligand orbitals (one from each
ligand) we are able to generate six orbitals of similar symmetry, called as ligand
group orbitals (LGO’s) as that of the six metals bonding orbitals. These orbitals on
the metal and the ligand now can combine to afford the MO diagram as shown below.

71
 The prominent features of this MO diagram:
• The lowest energy orbitals a1g, t1u, eg are closer in energy
to the ligand orbitals.
• The t2g orbitals remain non-bonding and their energy is
not changed after forming the MO’s.
• The higher energy orbitals a1g*, t1u*, eg* (antibonding
orbitals) are closer in energy to the metal orbitals.
• The energy separation between the non-bonding t2g and
the eg* orbitals represents the ∆o of the crystal field
diagram.
• As before, if this separation is large, low-spin complexes
are formed. If the separation is small, high spin
complexes are formed.
• Thus, [Co(NH3)6]3+ (Co3+ has six electrons; six ammonia
ligands contribute twelve electrons) has the electronic
configuration, a1g2, t1u6, eg4, t2g6.
Figure: An approximate MO diagram for the formation
of [ML6] (where M is a first row metal) using the
n+ • In contrast [CoF 6 ]3- has the configuration a 2, t 6, e 4,
1g 1u g
4
t2g eg* 2.
ligand group orbital approach. The bonding only
involves M-L σ-interactions. 72
 • The antibonding MOs are all
empty
• The complex should be
diamagnetic as all the electrons are
paired.
• The complex should be colored
since promotion of electrons from
the non-bonding MOs to the
antibonding eg* MOs is feasible.
• The energy jump Δo is 23000 cm-1.
The six non-bonding d electrons
are paired in this complex because
Δo is larger than the pairing energy
of 19 000 cm-1
• Thus [Co(NH3)6]3+ has no unpaired
electrons and is a low-spin
complex.

Figure: Molecular orbital diagram for [Co(NH3)6]3+. 73

 • The energies of the 2p orbitals on
F- are much lower than the energy
of the corresponding orbital on N
in NH3.
• This alters the spacing of the MO
energy levels.
• Spectroscopic measurements show
that Δo is 13 000 cm-1.
• Thus the gap between the non-
bonding MOs and the antibonding
eg*; MOs is less than the pairing
energy of 19 000 cm-1.
• Thus the non-bonding d electrons
do not pair up because there is a
net gain in energy if electrons are
left unpaired.
• Thus [CoF6]3- has foµr unpaired
electrons and is a high-spin
complex.
Figure: Molecular orbital diagram for [CoF6]3-. 74