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COURSE :
(LECTURE No. 1 TO 9)
COORDINATION COMPOUND - 2
[ x ]y
The chelate complexes are more stable than similar complexes containing unidentate ligands. The greater
stability of the chelate complex in comparison to normal complex is called chelate effect. For example,
Ni2+ (aq) + 6 NH3 (aq) [Ni(NH3)6]2+ (aq) Kformation = 108
2+
Ni (aq) + 3 NH2CH2CH2NH2(aq) 2+
[Ni(en)3] (aq) Kformation = 1018
The five and six membered rings are more stable.
ethylenediamine (en) or ethane -1, 2-diamine
The following are type and examples if ligands on the basis of this classification.
(a) Monodentate (one donor atom) :
F–, Cl–, Bl–, H O
2
: , N
H , CN– , NO – , OH–, CO, NO, C H N (py) etc.
3 2 5 5
(b) Didentate (two donor atoms : Some most common bidentate ligands are
COORDINATION COMPOUND - 3
NH2 CH CH2 NH2 (1, 2 propanediamine) (pn)
|
CH3
O O
C C
OR C2O42–
O O
2-
Oxalate ion (ox )
O O
C
CO32– OR || 2, 2 bipyridyl (bipy)
O
Carbonate ion
OR
OR
CH3 – C N – O –
| OR
CH3 – C N – OH
DIDENTATE CHELATION :
In [PtCl2(en)], en represents the didentate ligand, NH2CH2CH2NH2 (1,2-ethanediamine or ethylenediamine)
[Figure]
H2
Cl N
CH2
Pt
N CH2
Cl
H2
[PtCl2(en)]
(a)
COORDINATION COMPOUND - 4
(c) TRIDENTATE/TERDENTATE LIGAND/CHELATION :
H2N – CH – CH – N
H – CH – CH – N
H
2 2 2 2 2
CH2
CH2
H2N
Pt NH CH2
Cl N CH2
H2
+
[PtCl(dien)]
(b)
H2C – CH2
H H
N N
H2C Pt CH2
H2C N N CH2
H2 H2
2+
[Pt (trien)]
(c)
O O 3–
– O–C–CH CH2–C–O –
2
N–(CH2 )2–N
– O–C–CH
2
H
or
O
(Ethelenediaminetriacetato ion)
This acid is directly not soluble in water but its sodium salt is soluble.
O O 4–
: :
: :
:O C CH2 CH2 C O:
:N CH2 CH2 N: O
: :
: :
:O C CH2 CH2 C O: or
O O
EDTA4–, Ethylenediaminetetraacetate ion
Therefore, acid is not the ligand but its tetra anion is a ligand and its usual denticity is 6 but it is sometimes
also found to behave as tetradentate ligand and hence is a flexidentate ligand.
COORDINATION COMPOUND - 5
(g) FLEXIDENTATE LIGAND :
A polydentate ligand which is found to have different denticity in different coordination compounds is called a
flexidentate ligand. Note that in a particular complex denticity of a particular ligand is fixed, it can not be
flexible in the same compound.
EDTA can act as hexa, penta as well as tetra dentate ligand. For example ;
EDTA usually acts as hexadentate ligand but in [Cr(III)(OH)(EDTA)]2– and [Co(III)Br(EDTA)]2– as pentadentate
and in [Pd(II)H2(EDTA)]0 as a tetradentate ligand.
Sulphate ion, SO42– can also be mono or bi dentate ligand. For example ;
nitrito-N
M O—N=O nitrito-O
M SCN thiocyanato or thiocyanato-S
M NCS isothiocyanato or thiocyanato-N
COORDINATION COMPOUND - 6
LECTURE # 2
3. NOMENCLATURE OF COORDINATION COMPOUNDS :
We first are writing down the rules to write down the names of two impotant parts of a complex, first of ligands
and then that of central atom.
Naming of Ligands: The names of ligands are written according to the charge (+ , – or nuetral) on them.
Naming of Anionic ligands: the name of these ligands ends with –o. The name of anions can be of
following three types
1. If name of the anion ends with –ide then generally –e is replaced with –o
2. If the name of anion ends with –ate then –e is replaced with –o
3. If the name of anion ends with –ite then –e is replaced with –o
H– hydrido
O2– oxido
OH– hydroxido
X–
halido(chlorido, flourido, bromido, iodido)
O22– peroxido
O2– superoxido
O3– ozonido
N3– nitrido
N3– azido
NH2– amido
NH2– imido
CN– cyanido or cyanido–C (second is preferred)
NC– isocyanido or cyanido–N
[NCO]– cyanato –O or –N
[SCN]– thiocyanato–N or –S
NO2– nitro(is common when donation is through nitrogen)
–NO2 nitrito–N
–ONO nitrito–O
CH3COO– acetato
NO3– nitrato
S2O32– thiosulphato
SO4– sulphato
SO3– sulphito
HSO3– hydrogensulphito
HO2– hydrogenperoxido
(NOS)– thionitrito
S2– thio or sulphido
HS– hydrogensulphido(mercapto)
RSH mercatanes (greater affinity to mercury)
H2N – CH2COO– glycinato (gly)
acetylacetonato (acac)
o - phenanthroline (o-phen)
N.. ..N
urea
2, 2 bipyridyl (bipy)
Pb lead plumbate
Ag silver argentate
Au gold aurate
Sn tin stannate
Fe iron ferrate
Note : The name of central atom is not modified if the central atom is in the neutral part of the complex.
COORDINATION COMPOUND - 8
Steps for Writing the Name of a Complex :
(i) Calculate oxidation number of the central atom involved.
(ii) The cation is named first as is the case with other ionic compounds. This rule applies to both positively
and negatively charged coordination entities.
For example in K4[Fe(CN)6] and [Co(NH3)6]Cl3, K+ and [Co(NH3)6]3+ cations are named first.
Potassium hexacynidoferrate(II)
Hexaaminecobalt(III) chloride
(iii) Usually the number of free cation or anions is not given as can easily be calculated by charge balancing.
K4 [Fe(CN)6] [Co(NH3)6] Cl3
Potassium but not tetrapotassium Chloride but not trichloride
(iv) For writing the names of complex cation use the following rule.
Names of ligand in english alphabetical order with their qunatity as prefix (but do not use mono for one and
do not consider first letters of these number denoting prefixes in alphabetisation). This is followed by the
name of metal followed by its oxidation number (in Roman numeral) in a brackette like
(I), (II), (III), (O), (–I), (–II), etc.
[Co(NH3)4Cl2]+, pentaamminechloridocobalt(III).
(v) For writing the names of complex anion use the following rule.
Names of ligand in english alphabetical order with their qunatity as prefix (but do not use mono for one and
do not consider first letters of these number denoting prefixes in alphabetisation). This is followed by the
name of metal(modified as per rule already specified) followed by its oxidation number
(in Roman numeral) in a brackette. (I), (II), (III), (O), (–I), (–II), etc.
(NH4)2 [Co(SCN)4], ammonium tetrathiocyanato-S-cobaltate(II).
Note : When the names of the ligands include a numerical prefix or are complicated or whenever the use of
normal prefixes creates some confusion, it is set off in parentheses and the second set of prefixes is used.
2 di bis
3 tri tris
4 tetra tetrakis
5 penta pentakis
6 hexa hexakis
7 hepta heptakis
COORDINATION COMPOUND - 9
Na[Pt(NH3)BrCl(NO2)] Sodium amminebromidochloridonitrito–N–platinate(II)
K3[Al(C2O4)3] Potassium trioxalatoaluminate(III)
or Potassium tris(oxalato)aluminate(III)
[Co(NH3)6][Co(NH3)2(NO2)4]3 Hexamminecobalt(III) diamminetetranitrito-N-cobaltate(III)
[Fe(NCCH3)6]Br2 Hexakis(methylcyanide)iron(II) Bromide
[CuCl2 {O = C (NH2)2}2] Dichlorobis(urea)copper(III)
RULES FOR WRITING THE FORMULAE OF MONONUCLEAR COORDINATION COMPOUNDS :
Mononuclear coordination entities contain a single central metal atom. The sequence of symbols within the
formula of coordination entity is governed by the following rules :
(i) The central atom is listed first ;
(ii) The ligands are then placed in alphabetical order. The placement of a ligand in the list does not depend on its charge.
(iii) Polydentate ligands are also placed alphabetically. In case of abbreviated ligand, the first letter of the abbre-
viation is used to determine the position of the ligand in the alphabetical order. When ligands are polyatomic,
their formulas are enclosed in parentheses. Ligands abbreviations are also enclosed in parentheses.
(iv) The formula of the coordination entity is enclosed in square brackets.
(v) No space is kept between representations of ionic species within the formula ;
(vi) When the formula of a charged coordination entity is written without the formula of the counter ion, the charge
is indicated outside the square brackets as a right superscript with the number before the sign.
(vii) The charge of the cation(s) is balanced by the charge of the anion(s).
For example :
[Co(CN)6]3–, [Cr(H2O)6]3+ etc.
The following examples illustrate the above rules :
[Co(NH3)6]Cl3 ; [Co(NH3)5Cl]Cl2 ; K2[PtCl4]
[Co(NH3)4Cl(NO2)]Cl ; K3[Fe(CN)6] ; Na[AllII(H2O)2(OH)4]
Ex. Write the formulae for the following coordination compounds :
(i) tetrahydroxidozincate (II)
(ii) pentaaquachloridochromium (III) chloride
(iii) tetrabromidocuparate (II)
(iv) pentacarbonyliron (O)
(v) potassium tetracyanidocuprate (II)
Sol. (i) Zn(OH)4]2– (ii) [Cr(OH2)5Cl]Cl2 (iii) [CuBr4]2– (iv) [Fe(CO)5] (v) K2[Cu(CN)4]
Naming of Some Special Complexes and of Complexes with Bridging ligands :
Tetraaquacobalt(III)––amido––hydroxidotetramminechromium(III) sulphate
Some other examples are
COORDINATION COMPOUND - 10
(ii)
(iii) (SO4)2
di––hydroxidobis(tetraaquairon(III)) sulphate
(iv) (SO4)2
–amido––hydroxidobis(bis(ethylenediammine)cobalt(III)) sulphate
OR bis(ethylenediammine)cobalt(III)––amido––hydroxidobis(ethylenediammine)cobalt(III) sulphate.
Fe
The name of the above compund is bis(cyclopentadienyl)iron(II). This is commonly known as Ferrocene.
In the above compound the aromatic pi electron density of the ring is being donated to the Fe2+ ion, hence in
this way iron is bonded to all the five carbons of the upper flat ring and also to all five carbons of below flat ring.
This is also called a sandwich compound because of its shape. Its not a true complex this is an organome-
tallic compound which we study in detail in the last part of the chapter. To write down the formula of such
compound a special symbol is written before the name of such ligand and on superscript to this the
number of atoms is written between which the electron density is being shared. So the formula of this
compound will be Fe[ 5–C5H5]2 .
The other such example is bis(benzene)chromium which will be represented by the formula
Cr[ 6–C6H6]2
–
H H
C
Cl
Ti+4 C
Pt H H
Cl Cl
COORDINATION COMPOUND - 11
LECTURE # 3
BONDING IN COORDINATION COMPOUNDS :
(i) Initial bonding theories and EAN rule
(a) WERNER’S COORDINATION THEORY
The systematic study of coordination compounds was started by Alfred Werner whose pioneering work
opened an entirely new field of investigation in inorganic chemistry. He prepared and characterized a large
number of coordination compounds and studied their physical, chemical and isomeric behaviour by simple
experimental techniques. On the basis of these studies. Werner, in 1898, propounded his theory of coordina-
tion compounds.
The main postulates of Werner’s theory are :
Metals exert two types of linkages/valencies ; (i) the primary or ionizable links/valencies which are satisfied
by negative ions and equal the oxidation state of the metal and (ii) the Secondary or nonionizable links/
valencies which can be satisfied by neutral or negative ions/groups(or sometimes by cationic species -
discovered later). The secondary linkages equal the coordination number of central metal atom/ion. This
number is fixed for a metal.
The ions/groups bound by the secondary linkages have characteristic spatial arrangements corresponding
to different co-ordination numbers. In the modern terminology, such spatial arrangements are called coordi-
nation polyhedra. The various possibilities are
CN = 2 Linear
CN = 3 Triangular
CN = 4 Tetrahedral or sq. planar
CN = 6 Octahedral
The secondary valencies are generally represented by solid lines while the primary valencies are represented
by dashed lines and the ions which satisfy both primary and secondary valencies will be drawn with both
solid and dashed lines. For example the complex [CoCl (H2O)5] Cl2 is represented as
On the basis of the above postulates, Werner formulated the coordination compounds, CoCl3 . 6NH3, CoCl3
. 5NH3 and CoCl3 . 5NH3 and CoCl3 . 4NH3 as : [Co(NH3)6]Cl3, [CoCl(NH3)5]Cl2 and [CoCl2(NH3)4]Cl.
respectively - the species within the square brackets being the coordination entitles (complexes) and the
ions outside the square brackets the counter ions. He further postulated that octahedral, square, planar and
tetrahedral geometrical shapes are more common in coordination compounds of transition metals. Thus,
[Co(NH3)6]3+, [CoCl(NH3)5]2+, [CoCl2(NH3)4]+ are octahedral entities, while [Ni(CO)4] and [PtCl4]2– are tetrahe-
dral and square-planar, respectively.
Series of coloured compounds obtained by the interaction of aqueous CoCl3 and NH3
Compound Colour Name according to colour
CoCl3 . 6NH3 Yellow Luteo Complex
CoCl3 . 5NH3 Purple Purpureo Complex
CoCl3 . 4NH3 Green Praseo Complex
CoCl3 . 4NH3 Violet Violeo Complex
COORDINATION COMPOUND - 12
Werner used some experimental methods to find out the number of free ions and coordination number in
many different complexes. Such methods involved freezing point dpression measurement or boiling
point elevation measurement of aqueous solution of these complexes( we will study later about these
methods). Other methods included conductivity measurement of the aqueous solutions of these com-
plexes. Assume here that the conductivity of a solution only depends on the number of ions present per unit
volume or on concentration of the ions( which actually is not the case, we will study later that it also depends
on the nature of the on), try and arrange the solution of the following complexes in increasing order of
conductivity.
Secondary valency
S.No. Werner complex Modern notation Ionisation Primary valency satisfied by
satisfied by
3+
1 CoCl3.6NH3 [Co(NH3)6]Cl3 [Co(NH3)6] +3Cl
–
six (NH3) –
three (Cl )
– –
2 CoCl3.5NH3 [Co(NH3)5Cl]Cl2 2+ – – three (Cl ) including one (Cl )
[Co(NH3)5Cl] +2Cl five (NH3) and one (Cl )
with dual nature
–
+ three (Cl ) including
3 CoCl3.4NH3 [Co(NH3)4Cl2]Cl [Co(NH3)4Cl2] + Cl
– –
four (NH3) and two (Cl ) –
two (Cl ) with dual nature
4 CoCl3.3NH3 [Co(NH3)3Cl3] [Co(NH3)3Cl3] three (NH3) and three (Cl )
– –
three (Cl ) all with dual nature
From the above table it is clear that (i) the solution conductivity of complexes 1,2 and 3 corresponds to 1:3,
1:2 and 1:1 electrolyte respectively and thus the increasing order of the conductivity can be represented as
CoCl33NH3 < CoCl3. 4NH3 < CoCl3.5NH3 < CoCl3.6NH3 and (ii) the complexes 1,2 and 3 will react with silver
nitrate and give 3, 2 and 1 mole of the white precipitate of silver chloride.
Ex. For the compound represented by the formula CoCl3.5H2O write down the different complexes possible and
repesent them as per Werners notation and also write down their names.
Sol. CN = 6 octahedral
[CoCl(H2O)5]Cl2; [CoCl2(H2O)4]Cl.H2O; [CoCl3(H2O)3].2H2O;
generally water of crystallization is found with complexes which have bogth cationic and anionic parts, it is
less common with species which are neutral.
Ex. Match the pairs of complexes listed in column-I with the method(s) used for their differentiation
listed in column-II.
Column – I Column–II
(A) [Cr(H2O)6]Cl3 and Cr(H2O)5Cl] Cl2.H2O (p) Can be differentiated by amount, nature or
colour of precipitate formed.
(B) [Co(NH3)5Br]SO4 and [Co(NH3)5SO4]Br (q) Can be differentiated by electrical
conduction measurement method
(appreciable difference)
(C) [Co(NH3)5Cl]Cl2 and [Co(NH3)6]Cl3 (r) Can be differentiated using cryoscopic
measurement method.
(D) [Cu(H2O)4]SO4.H2O and [Cu(H2O)6](NO3)2 (s) Can be differentiated by heating with
concentrated H2SO4
Ans. (A) – p,q,r,s ; (B) – p,q ; (C) – p,q,r ; (D) – p,r,s
Sol. (A) [Cr(H2O)6]Cl3 (aq) [Cr(H2O)6]3+ (aq) + 3Cl– (aq)
[Cr(H2O)5Cl] Cl2.H2O (aq) [Cr(H2O)5Cl]2+ (aq) + 2Cl– (aq)
(b) [Fe2+(CN)6]4–
Number of electrons in Fe2+ = 26 – 2 = 24
6CN– = 6 × 2 = 12
So, EAN = 24 + 12 = 36 (krypton)
(c) [Fe3+(CN)6]3–
Number of electrons in Fe3+ = 26 – 3 = 23
6CN– = 6 × 2 = 12
So, EAN = 23 + 12 = 35
NOTE :
(a) The EAN rule is generally found to be not valid in case of most of the complexes but in case of metal
carbonyls( which is an important class of comlexes, we will be studying later) this rule is found to be valid in
all cases except one or two exceptions, so do remember it for metal carbonyls and do know how to calculate
the EAN for any metal.
(b) NO ligand is found to act as three electron donar, as indicated by the following reactions in which when the
carbonyl compound is heated in atmosphere of excess of NO.
[Fe(CO)5] + 2NO [Fe(CO)2(NO)2] + 3CO
[Cr(CO)6] + 4 NO [Cr(NO)4] + 6 CO
But also remember that NO+ is only two electron donar
The Werner theory and some other initial bonding theories cannot answer basic questions like.
(i) Why only certain elements possess the remarkable property of forming coordination compounds ?
(ii) Why the bonds in coordination compounds have directional properties ?
(iii) Why coordination compounds have characteristic magnetic and optical properties ?
COORDINATION COMPOUND - 14
LECTURE # 4
VALENCE BOND THEORY :
The valence bond theory, VBT, was extended to coordination compounds by Linus Pauling in 1931. The
basic principles involved in this treatment are :
(a) Metal will provide vacant orbitals depending on its CN. These vacant orbitals will be hybridised.
Thus hybrid vacant orbital of metal will overlap with the filled orbital of the ligand to form a coordinate bond.
(b) There is also found some kind of back bonding from metals to the ligands to maintain the charge neutrality.
The extent of this back bonding also depends on the nature of the ligand. We will study about this a bit in
metal carbonyls and all other complexes generally neglect this.
bond It is a partial bond between filled orbitals of metal & vacant of ligand.
The ligands which allow back bonding to sufficient extent are also called acid acceptors. For example
CO, CN–, NO etc.
(c) The type of hybridisation of metal & shape of complex involved can be decided conveniently if some chracteristics
of the complex like magnetic nature, geometry or whether exhibits isomerism or not etc. be known. Hence
along with the coordination number some other property must also be given to analyse the com-
plex using VBT.
sp3, dsp2, dsp3 and d2sp3 yield tetrahedral, square planar, trigonal-bipyramidal or square-pyramidal and octa-
hedral spatial arrangements commonly encountered in coordination compounds.
It is found that [Ni(CN)4]2–, is diamagnetic in nature. But we know that Ni2+ is paramagnetic with two
unpaired electrons, hence to be diamagnetic the electrons must have got paired up and one d orbital will be
available for the dsp2 hybridisation. For one d-orbital lobe available for hybridisation, pairing of electrons takes
place in the remaining d-orbitals, as shown below in the case of [Ni(CN)4]2–,
3d 4s 4p
Ni
Ni2+
[Ni(CN)4]2–
CN¯ CN¯ CN¯ CN¯
dsp2 hybrids used
[Ni(CN)4]2– is square planar and diamagnetic. [NiCl4]2–, on the other hand, is paramagnetic and has tetrahe-
dral geometry. In this case, the VB treatment assumes that (i) the d-orbital occupancy remains the same as
in the free Ni2+ ion and (ii) the metal uses sp3 hybrids (involving 4s and 4p orbitals) for bonding with the ligands
as shown below :
[NiCl4]2– is paramagnetic as there are two unpaired electrons.
3d 4s 4p
Ni
Ni2+
[Ni(CN)4]2–
Cl¯ Cl¯ Cl¯ Cl¯
3
sp hybrids used
The VB theory explains the formation of 6– coordinate, octahdral coordination entities by invoking the use of
(n-1)d2nsnp3 or nsnp3nd2 hybrid orbitals by the central metal ion in forming bonds with the ligands. Whether
the hybridisation is dsp3 or sp3d, it can be decided if number of unpaired e– or magnetic moment is known to
us else not. An example involving use of (n-1)d2nsnp3 hybrids is the coordination entity, [Fe(CN)6]4–, which is
found to be diamagnetic
The double occupancy of (n-1)d orbitals orbitals confers extra stability and the absence of unpaired electrons
renders this entity diamagnetic.
COORDINATION COMPOUND - 15
(n-1)d ns np
Fe
Fe2+
[Fe(CN)6]4–
L L L L L L
(d2sp3 hybrid orbitals filled by electron pairs donated by the respectively ligands. L = CN¯).
Ex. Predict the number of unpaired electrons in the square planar [Pt(CN)4]2– ion.
Sol. Pt2+ is a 5d8 ion. For square-planar geometry, dsp2 hybrids are required. For the availability of one d orbital,
pairing of electrons takes place in the remaining d-orbitals. Hence there are no unpaired electrons in [Pt(CN)4]2–
ion.
Ex. For the comlex [Ma2 b2], It is given that it does not show geometrical isomerism. Predict the hybridisation.
Sol. CN = 4
Hence either square planar( dsp2 ) or tetrahedral( sp3 ) but since no geometrical isomerism, hence must be
tetrahedral( sp3 ).
CN = 3 The most important geometries for the complexes with CN = 3 are trigonal planar and the trigonal pyramidal.
Examples are the planar HgI3– and [Cu(CN)3]2– and the pyramidal SnCl3–.
Ex. [Hg2+3–3]–1
C.N. = 4 This is one of the most important coordination number and results in tetrahedral and square planar geom-
etry.
Ex. Ni (CO)4 (liquid), is found to be diamagnetic, explain the shape and hybridisation.
Sol.
Ex. [NiCl4]2–, is found to be paramagnetic with two unpaired electrons, explain the shape and the hybridisation.
COORDINATION COMPOUND - 16
Sol. Tetrahedral
CN– are strong field ligands (will study in CFT) and therefore they will force the 3d8 electrons to pair up in 4
orbitals.
CN = 5 Coordination number five is less common than coordination number four or six, the possible geometries are
trigonal bipyramidal and the square pyramidal. In most of the complexes these geometries are also found to
interchange into each other. For both these geometries sp3d and dsp3 are two possible hybridisations.
Ex. [Fe(CO)5], this complex is founf to have its total dipole moment to be equal to zero. Explain the hybridisation.
Ex. [Ni(CN)5]3– is found to be dimagnetic with 2 types of Ni – C bond lengths out of which four bond lengths are
found to be equal and the fifth one is different. Explain the hybridisation, shape and thus the observed
properties.
Sol. CN = 5
COORDINATION COMPOUND - 17
CN = 6 This is the most common coordination number and the geometry associated is octahedron. For hybridisation
there are two possibilities
sp3d2 or d2sp3
Ex. [Fe(CN)6]4– complex is found to be diamagnetic while the [Fe(CN)6]3– complex is found to be paramagnetic
with one unpaired electron. Explain the shape and hybridisations of both.
Sol. [Fe(CN)6]4–
[Fe3+(CN)6]3–
Ex. [FeF6]3– complex is found to be highly paramagnetic with five unpaired electrons, explain the shape and
hybridisation.
Sol. Fe3+ 3d5
COORDINATION COMPOUND - 18
LECTURE # 5
(III) CRYSTAL FIELD THEORY :
The Crystal Field Theory (CFT) was originally proposed for explaining the optical properties of crystalline
solids.It was applied to the study of coordination compounds in the 1950s. CFT assumes the ligands to be
point charges and the interaction between them and the electrons of the central metal to be electrostatic in
nature. The five d-orbitals in an isolated gaseous metal atom/ion have same energy, i.e., they are degener-
ate. This degeneracy is maintained if a spherically symmetrical field of negative charges surrounds the metal
atom/ion. However, when this negative field is due to ligands (either anions or the negative ends of dipolar
molecules like NH3 and H2O) in a complex, it becomes asymmetrical and the degeneracy of the d-orbitals is
lifted. It results in splitting of the d-orbital energies. The pattern of splitting depends upon the nature of the
crystal field. We will first consider :
d ,d
x
2 y 2 z2
or eg
axial d orbitals
For convenience, let us assume that the six ligands are positioned symmetrically along the cartesian axes,
with the metal atom at the origin. As the ligands approach, first there is an increase in the energy of d orbitals
to that of the free ion just as would be the case in a spherical filed. Next, the orbitals lying along the axes (dz2
and dx 2 y 2 ) get repelled more strongly than dxy, dyz and dxz orbitals, which have lobes directed between the
axes. The d xy , d yz , dxz orbitals are lowered in enrgy relative to the average energy in the spherical crystal
filed. Thus, the degenerate set of d orbitals get split into two sets : the lower energy orbitals set, t2g and the
higher enrgy, eg set. The energy seperation is denoted by 0 (the subscript o is for octahedral (Fig.)
COORDINATION COMPOUND - 19
Let us now learn about the significance od 0 by considering first the d1 coordination entity, [Ti(H2O)6]3+,
formed in aqueous solutions of Ti3+ (d1) ion. Obviously, the single d electron occupies one of the lower energy
t2g orbitals. In d2 and d3 coordiantion entities, the d electrons occupy the t2g orbitals singly in accordance with
the Hund’s rule. For d4 ions, two possible patterns of electron distribution arise : i) the fourth electron may
enter an eg orbital (of higher energy) or ii) it may pair an electron in the t2g level. The actual configuraion
adopted is decided by the relative values of 0 and P. P represents the enrgy required for electron
pairing in a single orbital.
If is less than P (0 < P), we have the so called weak field, high spin situaiton, and the fourth electron
3 1
entres one of the eg orbitals giving the configuraiton t 2g eg . If now a fifth electron is added to a weak field
3 2
coordination entity, the configuraiton becoms t 2g eg .
When 0 > P, we have the strong field, low spin situation, and pairing will occur in the t2g level with the eg
level remaining unoccuped in tentities of d1 to d6 ions. Calculations show that coordination entities with
four to seven d electrons are more stable for strong field as compared to weak field cases.
This extra stabilization due to ligand field in comparison to normal situation( if there would have been no
spilitting or if there would have been spherically symmetrical ligand field) is called CFSE(Crystal field
stabilization energy). This CFSE can be calculated as follows
General formula : CFSE = [– 0.4 (n) t2g + 0.6 (n) eg] o + nP.
where n & n are number of electron(s) in t2g & eg orbitals respectively and o crystal field splitting energy for
octahedral complex. n represents the number of extra electron pairs formed because of the ligands in
comparison to normal degenerate configuration.
COORDINATION COMPOUND - 20
SPECTROCHEMICAL SERIES
On the basis of the behaviour (the splitting produced with different metal ions) of ligands these are arranged
in a series according to their strentgh which is called Spectrochemical Series.
weak Ligand
I–<Br– < S2– < SCN– < Cl– < NO3 < N3 < F– < OH– < C2O24 < H2O <
NCS– < CH3CN < Py < NH3 < en < bpy < NO 2 < PPh3 < CN– < CO
Strong Ligand
Do note one thing in the series that in all strong field ligands the donor atom is either Nitrogen atom or
Carbon atom while in all weak field ligands the donar atoms are either Oxygen atoms or Sulphur or halogen
atoms.( Remember)
The intermediate ligands can in some cases act as strong field ligands or can also act as weak field ligands
depending on the nature of the metal involved or some other factors. Generally for kexamples in our
course we can consider ligands upto water as weak and beyond water as strong. But do remember
the following exception.
Ex. [Co(C2O4)3]
Co3- 3d6 t2g2, 1, 1 eg 1,1
If C2O24 is considered W.L. sp3d2 and paramagnetic with four unpaired electrons.
high spin /outer orbital complex.
If C2O24 is considered S.L d2sp3 and diamagnetic
t2g2,2,2 eg 0,0 low spin/inner orbital complex.
Ex. What is electronic configuration of Fe2+ in complex [Fe(CN)6]4– and in complex [FeF6]3–
Sol. [Fe(CN)6]4– Fe+2 3d6 t2g2,2,2 eg0,0 d2sp3
Ex. In the complex [Fe(Cl)(CN)4(O2)]4– , the electronic configuration of metal ion in this ligand field is found to be
t2g2,2,2, eg0,0. Then find out whether the complex is paramagnetic or diamagnetic and whether the O–O bond
lentgh in the complex is more than that in dioxygen O2. Also write the IUPAC name of the complex.
Sol. 3d6 Fe2+ O21 superoxido
Bond order = 1.5
Diamagnetic Paramagnetic (1)
B.L. more than O2
Chlorotetracyano superoxidoferrate (II) ion.
COORDINATION COMPOUND - 21
LECTURE # 6
(B) CRYSTAL FIELD EFFECTS IN TETRAHEDRAL COORDINATION ENTITIES :
In tetrahedral complexes none of the ligand is directly facing any orbital so the splitting is found to be small
in comparison to octahedral complexes. For the same metal, the same ligands and metal-ligand distances,
it can be shown that t = (4/9)o. This may attributes to the following two reasons.
(i) there are only four ligands instead of six, so the ligand field is only two thirds the size ; as the
ligand field spliting is also the two thirds the size and (ii) the direction of the orbitals does not
concide with the direction of the ligands. This reduces the crystal field spliting by roughly further
2 2 4
two third. So t = × = o.
3 3 9
Consequently, the orbital splitting energies are not sufficiently large for forcing pairing and, there-
fore, low spin configurations are rarely observed.
2
2
Ex. Ni Cl4 calculate the CFSE of this tetrahedral complex.
Sol. Ni2+ 3d8 4s0p0
Weak filed ligand
Configuration of Ni(II) in tetrahedral field P = eg2, 2, t2g 2,1,1
t P(2)
For square planar geometry one d-orbital must be vacant.
So hybridisation sp3
3 2
CFSE = 4 × t + 4 t = – 2.4 t + 1.6 t = – 0.8 t.
5 5
In tetrahedral complexe, all ligands are considered to be weaker ligands and, therefore, electrons filling takes
place continuously from equal to t2g.
[MnO4]– d3s / sp3
permanate tetrahedral
ion
COORDINATION COMPOUND - 22
FACTORS FAVOURING TETRAHEDRAL COMPLEXES :
Tetrahedral complexes are favoured by steric requirements, either simple electrostatic repulsion of charge
ligands or vander wall's repulsions of large one. A valence bond (VB) point of view ascribed tetrahedral
structure to sp3 hybridisation.
Tetrahedral complexes are thus generally favoured by large ligands like Cl–, Br–, – and PPh3 and metal ions
of six types ;
(1) those with a noble gas configuration such as Be2+ (nsº) ;
(2) those with pseudo noble gas configuration (n–1)d10 ns0np0, such as Zn2+, Cu+ and Ga3+, and
(3) those transition metal ions which do not strongly favour other structure by virtue of the CFSE, such
as Co2+, d7.
(4) those transtion metal which have lower oxidation state.
(5) those metals generally with electronic configuration dº, d5 and d10 perfer to form such complexes.
(6) It is abserved that
Sc Ti V Cr Mn Fe Co Ni Cu Zn
usually form tetrahedral form tetrahedral
complexes with oxo ligands complexes with hallide ions
eg. : [CrO4]2– , [MnO4]2– [FeO4]2– eg. : [NiCl4]2– , [CuCl4]2–
Examples :
2 2
2 2
3d10 , [ Z n(NH3 )4 ] ; 3d10 , [ Zn(CN)4 ] CFSE = O (diamagnetics)
[Ni(CO)4] diamagnetics
[NiCl4]2– paramagnetics with two unpaired electrons.
[NiCl2 (pph3)2] paramagnetics with two unpaired electrons.
[MnCl4]2– paramagnetics with five unpaired electrons.
[FeCl4]2– paramagnetics with four unpaired electrons.
[Cu(py)4]+ diamagnetics.
Cs2 [CuCl4] orange tetrahedral paramagnetics with one unpaired electrons.
(NH4)2 [CuCl4] yellow square planaer paramagnetics with one unpaired electrons.
COORDINATION COMPOUND - 23
The value of sp has been found larger than o because of the reason that dxz and dyz orbitals interact with only
two ligands in the square planar complexes, while in octahedral complexes the interaction takes place only
with four ligands. sp has been found equal to 1.3o.
COORDINATION COMPOUND - 24
Examples :
(i) [Ni(CN)4]2– D
(ii) [Ni(en)2]2+ D
(iii) [Ni(dmg)2]0 D
(iv) [PtCl4 ]2– D
(v) [Pt(NH3)4]2+ D
(vi) [AgF4]– D
(vii) [RhCl(PPh3)2 ]0 D Wilkinson catalyst. (hydrogenation of Alkenes)
(viii) [Ni(CR)2 (PMe3)2] D
Important factors which determine the magnitude of the orbital splitting energy, are :
(i) Oxidation state of the metal ion : Generally, the higher the ionic charge on the central metal ion, the
greater the value of .
(ii) Nature of the metal ion : For analogous entities within a group, the values differ. The general trend
being 3d < 4d < 5d. Thus while going from Cr to Mo or Co to Rh, the 0 value increases by ~ 50%. As a
consequence of this, coordination entities have a greater tendency to be low spin as compared to the first
transition series.
(iii) Geometry of the coordination entity : The t value is only ~ 50% as large as that of 0.
sp > 0 > t
approximately, for the same set of ligands
sp 1.3 0
4
t
9 0
(iv) Nature of the ligand : The ligands can be arranged in the order of increasing field strength.
With strong field ligands, increases
With weak field ligand, decreases.
COORDINATION COMPOUND - 25
LECTURE # 7
5. SOME PROPERTIES OF COORDINATION COMPOUNDS :
(a) COLOUR IN COORDINATION COMPOUNDS :
Coordination compounds of transition metals have fascinating colours. According to the crystal field theory
the colour is due to the d-d transition of electron under the influence of ligands. We know that the colour of a
substance is due to the absorption of light at a specific wavelength in the visible part of the electromagnetic
spectrum (400 to 700 nm) and transmission or reflection of the rest of the wavelengths. An object that
absorbs all visible light appears black. The mechanism of light absorption in coordination compounds is that
photons of appropriate energy can excite the coordination entity from its ground state to an excited state.
Consider the Ti(III) ion in solution, that is [Ti(H2O)6]3+. This is a violet colour octahedral complex, where in the
ground state of the complex a single electron is present in t2g level. The next higher state available for the
transition is the empty eg level. If the light corresponding to the energy of yellow-green is absorbed by the
complex, it would excite the electron from t2g level to eg level. Consequently the complex appears violet in
colour. In case of copper (II) ions in solution, for example, it can be imagined that one of the d-electrons from
the t2g set (dxy, dyz, dxz) gets excited to the eg set ( d x 2 y 2 ,d z 2 orbitals). In this case since high energy is
transmitted it means that low energy light (red region) is absorbed. For copper (II) ions in aqueous solution,
the energy gap 0 is relatively small. Table below gives the relationship of the wavelength absorbed and the
colour observed.
By using spectroscopic data for a number of coordiantion compounds having the same metal ion but different
ligands, the crystal field splitting for each ligand has been calculated and the spectrochmeical series has
been prepared.
Relationship between the wavelength of light absorbed and the colour observed In some
coordination entitles
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
Coordination entity Wavelength of light Colour of light Colour of coordination
absorbed (nm) absorbed entity
––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
[CoCl(HN3)5]2+ 535 Yellow Violet
[Co(NH3)5(H2O)]3+ 500 Blue Green Red
[Co(NH3)6]3+ 475 Blue Yellow Orange
[Co(CN)6]3- 310 Ultraviolet Pale Yellow
2+
[Cu(H2O)4] 600 Red Blue
[Ti(H2O6)3+ 498 Blue Green Purple
–––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––––
You need not remember the above table, you will be provided with it whenever the question is asked and also
you need not remember the color of the complexes except some common complexes which will be used in
qualitative analysis and hence in detection of different ions.
Note : (a) In absence of ligand, crystal field splitting does not occur and as a consequence the substance
appears colourless. For example (i) removal of water from violet coloured complex [Ti(H2O)6]Cl3 on heating
makes it colourless. (ii) Similarly anhydrous copper sulphate (CuSO4) is white, but hydrated copper sulphate
(CuSO4.5H2O) is blue coloured.
(b) The nature of the ligand and the molar ratio of metal : ligand also influence the colour of the complex for
example in the pale green complex of [Ni(H2O)6], the colour change is absorbed when ethylenediamine is
progressively added to it.
Note : Ruby is Al2O3 in which 0.5–1% Cr3+ ions (d3 electron system) are randomly distributed in the positions
normally occupied by Al3+. We may consider Cr(III) species as octahedral Cr(III) complexes incorporated into
COORDINATION COMPOUND - 26
the alumina lattice ; d-d transition of electron at these centres give rise to the colour (red).
Emerland is the mineral beryl (Be3Al2Si6O18) in which Cr3+ ions occupy octahedral sites, but in this case low
energy corresponding to yellow red and blue is absorbed and light corresponding to green region is transmitted.
COORDINATION COMPOUND - 27
MLn–1 (H2O) + L MLn + H2O Kn = [MLn] / {[MLn–1 (H2O)] [L]}
n, the stability constant, is related to thermodynamic stability when the system has reached equilibrium.
Most of the measurements have been made from aqueous solutions, which implies that the complex is
formed by the ligand displacing water from the aqua complex of the metal ion. Ignoring the charge and taking
L as un unidentate ligand, the stepwise formation of the complex is represented as shown above. K1, K2, K3
..... Kn representing the stepwise stability (or formation) constants.
The above is thermodynamic stability criteria, there can be another kind of stability called Kinetic Stability,
which measures the rate of ligand replacement.
The value of stability constant for some of the complexes are given below:
Complex Stability constant
[Cu(NH3)4]2+ 4.5 × 1011
[Ag(NH3)2]2+ 1.6 × 107
[Co(NH3)6]2+ 1.12 × 1011
[Co(NH3)6]2+ 5.0 × 1033
[AgCl2]– 1.11 × 105
[AgBr2]– 1.28 × 107
[Ag(CN)2]– 1.0 × 1022
[Cu(CN)4]2– 2.0 × 1027
[Fe(CN)6]3– 7.69 × 1043
The above table is only for teachers information, we dont expect the students to remember the constants or
the order of stability of the complexes.
Important generalizations derived from the vast data on stability constants are :
For a given metal and ligand the stability is generally greater, the greater the charge on the metal
ion. Thus, stability of coordination entities of ions of charge 3+ is greater than the entities of 2+ ions. Further,
for the divalent ions of the first row transition elements, irrespective of the ligand involved, the
stabilities vary in the Irving-Williams order :
MnII < FeII < CoII < NiII < CuII > ZnII
This order is according to the size of the ions, smaller the size of the ion or greater the charge density on the
metal greater is the stability of the complex.
The stability also depends on the formation of chelate rings. If L is an unidentate ligand and L–L, a
didentate ligand and if the donor atoms of L and L–L are the same element, then L–L will replace
L. The stabilisation due to chelation is called the chelate effect. It is of great importance in biological
systems and analystical chemistry. The chelate effect is maximum for the 5- and 6-membered rings. In
general, rings provide greater stability to the complex.
If a multidentate ligand happens to be cyclic and there are no unfavourable steric effects, a further increase
in stability occurs. This is termed the macrocyclic effect.
COORDINATION COMPOUND - 28
LECTURE # 9
6. ISOMERISM IN COORDINATION COMPOUNDS :
(i) Structural Isomerism :
(A) IONISATION ISOMERISM :
This type of isomerism occurs when the counter ion in a coordination compound is itself a potential ligand.
Thus, the pairs of the following compounds :
(i) [Co(NO3)(NH3)5]SO2, and [Co(SO4)(NH3)5](NO3)
(ii) [PtCl2(NH3)4]Br2, and [PtBr2(NH3)4]Cl2 produce different ions in solution.
(iii) [Co(en)2(NO2)Cl]SCN, [Co(en)2(NO2)SCN]Cl and [Co(en)2(SCN)Cl]NO2
A special form of ionisation isomerism is the so called Hydrate isomerism. It occurs when water forms a
part of the coordination entity or is outside it. For example, CrCl3 . 6H2O exists in three distinct isomeric
forms : [Cr(H2O)6]Cl3, violet ; [CrCl(H2O)5]Cl2.H2O, pale green : [CrCl2(H2O)4]Cl.2H2O, dark green. Apart from
their distinctive colours, the three isomers can be identified by the addition of excess of aqueous silver nitrate
to their aqueous solutions, which precipitates chloride in the molar ratio of 3 : 2 : 1 respectively.
Complex Reaction with AgNO3 Reaction with conc. H2SO4(dehydrating agent)
[Cr(H2O)6]Cl3 in the molar ratio of 3:1 No water molecule is lost or no reaction
[CrCl(H2O)5]Cl2.H2O in the molar ratio of 2:1 one mole of water is lost per mole of complex
[CrCl2(H2O)4]Cl.2H2O in the molar ratio of 1:1 two mole of water is lost per mole of complex
COORDINATION COMPOUND - 29
(ii) Stereoisomerism :
Geometrical Isomerism :
GEOMETRIC ISOMERISM :
First we consider the cases of coordination number 4. The tetrahedral compounds can not show geometrical
isomerism as we all know that all four positions are equivalent in tetrahedral goemetry. So moving on to
square planar complexes there are different possibilities depending upon the formula of the compound. So
we are taking the different cases in sequence
(a) Square planar complexes with all monodentate ligands
In all following examples, we will be representing metal atom by symbol M, monodentate ligands
by small letters a, b, c, d, e, f ... etc and the symmetrical bidentate ligands are by AA, BB, CC etc
while the umsymmetrical bidentate ligands by AB, CD.. etc.
Formula No. of GI’s Trans pairs
Ma4 No GI (aa)(aa)
Ma3b No GI (aa)(ab)
Ma2 b2 M M
a b b a
Cis trans
Ma2bc M M
a c b a
Cis trans
Mabcd 3 (ab)(cd) aTb
(ac)(bd) aTc
(ad)(bc) aTd
a b a d
Mabcd M M
d c c b
aTc aTb
a b
c d
aTd
COORDINATION COMPOUND - 30
(b) Square planar complexes with one bidentate ligand and other two monodentate ligands
Complex No.of geometrical isomers Trans pairs
M(AA)a2 0 (Aa)(Aa)
M(AA)ab 0 (Aa)((Ab)
M(AB)a2 0 (Aa)(Ba)
M(AB)ab 2 (Aa)(Bb)
(Ab)(Ba)
A a A b
M M
B b B a
M(AA)2 0 (AA)(AA)
M(AB)2 2 (AB)(AB)
(AA)(BB)
A A A B
M(AB)(AB) M M
B B B A
M(AA)(BB) 0 (AB)(AB)
M(AA)(CD) 0 (AC)(AD)
M(AB)(CD) 2 (AC)(BD)
(AD)(BC)
A C A D
M(AB)(CD) M M
B D B C
ATD ATC
COORDINATION COMPOUND - 31
LECTURE # 8
CN = 6 (Octahedral Complexes)
Again the different cases possible are
i Ma6
no.G.I only one form is possible ( both will be optically inactive)
ii Ma5b
(iii) Ma2b4 – 2 (aa)(bb)(bb) (optically inactive)
(ab)(ab)(bb) (optically inactive)
b b a
b a b a b b
Ma2b4 M M
|||
M
b a a b b b
b b a
a c b
a b a b a a
M M
|||
Ma4bc M
a c a a a a
a a c
Cis Trans
b b
a b a b
Ma3b3 M M
a a a
b
a b
COORDINATION COMPOUND - 32
Like [Co(NO2)3(NH3)3]. If each trio of donor atoms occupy adjacent positions at the corners of an octahedral
face, we have the facial (fac) isomer. When the positions are around the meridian of the octahedron we, get
the meridional (mer) isomer
b b
a b b a
M M
a b a a
a b
Fac- (a) Mer-
NH3 NH3
O2N NH3 H2N NO2
Co Co
NO2 NO2
Fac- Mer-
(b)
(vi) Ma3b2c – 3
The trans pairs for the three isomers are
(aa)(ab)(bc) (optically inactive)
(aa)(bb)(ac) (optically inactive)
(ab)(ab)(ac) (optically inactive)
(vii) Ma3bcd – 4
The trans pais for the four possible isomers are
(aa)(ab)(cd) (optically inactive)
(aa)(ac)(bd) (optically inactive)
(aa)(ad)(bc) (optically inactive)
(ab)(ac)(ad) (optically active)
(viii) Ma2b2c2 – 5
The trans pairs for the possible isomers are
(aa)(bb)(cc) (optically inactive)
(aa)(bc)(bc) (optically inactive)
(bb)(ac)(ac) (optically inactive)
(cc)(ab)(ab) (optically inactive)
(ab)(ac)(bc) (optically active)
COORDINATION COMPOUND - 33
(ix) Ma2b2cd – 6
(x) Ma2bcde – 9
(xi) Mabcdef – 15
a
a A
a A
b a
A a A a
M(AA)a3b – 2 M M
A a A b
b a
bTa aTa
a a b
A b A a A
M(AA)a2b2 – 3
M M M
A b A b A
a b b
M(AA)abcd – 6
M(AA)3 – 1 form (No G.I.)
MI(AB)3 – 2 form
A A
A A A B
Fac. M Mer. M
B B B B
B B
COORDINATION COMPOUND - 34
Optical isomerism (is in the NCERT text so will be covered) :
A Coordination compound which can rotate the plane of polarised light is said to be optically active.
When the coordination compounds have same formula but differ in their ability to rotate directions of
the plane of polarised light are said to exhibit optical isomerism and the molecules are optical isomers.
The optical isomers are pair of molecules which are non-super impossible mirror images of each other.
This is due to the absence of elements of symmetry in the complex.
(A) Optical isomerism is very common in octahedral complexes.
(a) [Ma2B2C2]n± Out of five different geometrical isomers, only one is optically active
[Pt(py)2(NH3)2Cl2]2+
[Pt(py)NH3NO2ClBrI]
py py
py NO2 O2 N py
Pt Pt
Cl NH3 H3 N Cl
I I
d-isomer Mirror l-isomer
3+ 3+
en en
en
Co Co
en
en en
d-form Mirror l-form
COORDINATION COMPOUND - 35
(e) [M(AA)2ab]n± (Co(en)2NH3Cl]2+
N en + en N +
H3N N N NH3
Cr Cr
H3N Cl Cl NH3
Cl Cl
METAL CARBONYLS :
A widely studied and important class of organometallic compounds is that of metal carbonyls. Binary com-
pounds of metals with CO are called metal carbonyls. The homoleptic carbonyls (compounds containing
carbonyl ligands only) are formed by most of the transition (d metals). The metals constituting the central
part of the d block form stable, neutral binary
carbonyls like : [V(CO)6], [Cr(CO6], [Mo(CO)6],
[W(CO6], [Mn2(CO)10], [Fe(CO)5], [Fe2(CO)9],
[Co2(CO)8], [Co4(CO)12], [Ni(CO4)], etc. Outside
the central part of d-block, the metal carbonyls
are usually unstable.
COORDINATION COMPOUND - 36
Structures of some representative homoleptic metal carbonyls.
Metal carbonyls are mostly solids at room temperature and pressure. Exceptions being iron and nickel
carbonyls which are liquids. The mononuclear carbonyls are vaolatile and toxic. With the exception of Fe2(CO)9,
enneacarbonyldiiron(o), carbonyls are soluble in hydrocarbon solvents. Mononuclear carbonyls are either
colourless or light-coloured. For example, Fe(CO)5 is light straw-coloured liquid. Polynuclear carbonyls are
more deeply coloured. Fe3(CO)12, dodecacarbonyltriiron(o), for example, is a deep grass green solid. The
reactivity of metal carbonyls is due to (a) the metal centre of the carbonyl, and (b) the CO ligands. Metal
carbonyls find use as industrial catalysts and as precursors in organic synthesis.
The bonding in organometallic compounds in general and in carbonyls in particular is best explained by the
molecular orbital theory.
Carbon monoxide, CO, as a ligand binds itself to metal atoms through the carbon atom. It is a
weak donor (a weak base). It forms a weak bond to the central atom. CO is also an acceptor
ligand and froms a bond to the metal. This characteristic property of back bonding stabilised the
metal-ligand interaction.
For a better understanding of the nature of bonding in metal carbonyls, we have to consider first the
molecular orbital energy level diagram of carbon monoxide given in the figure. 3, the highest occupied
molecular orbital in CO is essentially a lobe projecting away from the carbon atom. When CO acts as a
lgand. This orbital serves as a weak donor to the metal atom, and forms a bond as represented in Figure. The
lowest unoccupied molecular orbltals of CO are the * (2) orbitals. These play an important part in bonding
as they can overlap metal d orbltals having symmetry. The resultant Interaction leads to the delocalisation
of electrons from, filled d orbltals on the metal into the empty orbitals on the CO ligands.This in fact, is back
bonding from metal to CO. The metal to ligand bonding creates a synergic effect which strengthens the bond
between CO and the metal (Figure).
The MO energy level diagram for CO The filled 3 and the vacant 2 oribttols are important
for bonding in the formation of metal carbonyls.
M C O
COORDINATION COMPOUND - 37
Synergic bonding
Example of synergic bonding interactions in a carbonyl complex.
(i) As M — C bonding increases, the C — O bond becomes weaken. The greater the positive charge on the
central metal atom, the less readily the metal can donate electron density into the * orbitals of the carbon
monoxide ligands to weaken the C — O bond.
(ii) In contrast, in the anionic complex (i.e. carbonylate anion) the metal has a greater electron density to be
dispersed, with the result that M — C bonding is enhanced and the C — O bond is diminished in strength.
For example in isoelectronic complexes the strength of metal-ligand bond increases and strength of C — O
bond in CO decreases (because bond order decreases) as the negative charge on the complexes increases.
Thus order of CO bond strengths ;
(a) [M(CO)6]+ > [Cr(CO)6] > [V(CO)6]– > [Ti(CO)6]2–.
(b) [Ni(CO)4] > [Co(CO)4]– > [Fe(CO)4]2–.
Classification of metal carbonyls
Ni(CO) 4
Fe(CO)5 Fe 3 (CO)12
3d
Cr(CO)6 Mn2CO10 CO 4 (CO)12
V(CO)6
Mo(CO)6
4d
Ru(CO)5
W (CO)5
5d
Os(CO)6
Note : Besides the metal carbonyls, there are some metal carbonyl anions which generally form salts with alkali
metal ions.
Ex : Na[V– (CO)6]–1 Sodium hexacarbonyl vanadate (–I)
K2[Ni2(CO)6]
Octahedral
H H –
C
||
Cl C
K [PtCl3 (2 – C2H4 )] K+
Pt H H
Cl Cl
COORDINATION COMPOUND - 39