C H A P T E R

15
Lanthanides lhus Ce ij Pr ufn;k Nd izse dh Pm lek;h Sm ;w Eu xnxn Gd rc Tb fny Dy gqvk Ho vjs Er rqe Tm ;w gh Yb yktokc gks Lu

CO-ORDINATION CHEMISTRY
LEARNING TECH.
Actinides rkaxs iS mueas utjsa iM+h vkleka fleVk fctyh pedh ,glku Qjkeks'k eapyh fudyh yM+dh Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr

d-Block lqjs'kpanz
Sc Y

frokjh
Ti Zr

VCR
V Nb Ta

eas

QSa
Fe Ru Os

dks
Co Rh Ir

ugha
Ni Pd Pt

ihry
Cu Zn Ag Au Cd Hg

Cr Mn Mo Tc W Re

;kj
La

tjk
Hf

uacj feyk rk ------jk------jk-----gQ~rk oks

Cu Ag Au

yk
fudkg i<+ks iafMr Ni Pd Pt

jksbZ dher c<+rh gSA

Zn tekuk Cd dnznku Hg gksxk

298 S L : AT (1) The compound, which contains acidic or basic radicals is known as salts. (2) The compound, which is formed by the neutralisation reaction of acid and base is known as salt. (3) The compound, which on hydrolysis gives acid and base is known as salt.

INORGANIC CHEMISTRY

TYPEOFSALTS: (1) Simple salt: The salt, which contains one type of simple positive ion and one type of simple negative ion. For example, NaCl, KCl and Na 2CO3. (2) Mixed salt: The salt, which contains more than one type of positive ions or more than one type of negative ions or both the ions are more than one type. For example, microcosmic salt, NaNH4HPO4.4H2O. (3) Double salt: When two simple salt equimolar aqueous solutions are mixed together in equal amount and then are allowed to evaporate, then residue which will left is known as double salt. When we ionize this salt, we will get three types of ions. In double salt one ion should be common, either it should be positive ion or negative ion. For example, and (ALUM) K2SO4, Al2(SO4)3, 24H2O and (MOHR SALT) (NH4)2SO4.FeSO4.6H2O. (4) Complex salt: The salt, which contains at least one complex ion or both the ions are complex in nature is known as complex salt. For example, K4[Fe(CN)6], [Cr(H2O)6]Cl3 and [Pt(P4)6][PtCl4]. INTRODUCTIONTOCO-ORDINATIONCHEMISTRY

Ligand are electron pair donor as well as electron pair acceptor groups but carbonyl is the only the ligand which can donate as well as accept electron pair. Except this ligand, generally other ligands are electron pair donor groups. CLASSIFICATIONOFLIGANDS (1) Charges resent on ligand: Ligands are of three types depending upon the charges present on them: (a) Negative ligands Ligands having negative charge on it and suffix 'O' will be added. Cl Br F OH NH2 NH N H C2O42 Chloro Bromo Fluoro Hydroxo Amido Imido Nitrido Hydrido Oxalato CO32 SO42 NO2 ONO NO3 NCS SCN Carbanato Sulphato Nitro Nitrito Nitrato Thiocynato-'N' Thicynato-'S' (b) Neutral ligands Ligand having no charge and it has no suffix/prefix. NH3 H2O CO CS NO NS Amine Aqua Carbonyl Thiocarbonyl Nitrosyl Thionitrosyl (c) Positive ligands Ligand having positive charge on it and 'ium' suffix will be added. NO+ NO2+ NH2NH3+ Nitrosonium Nitronium Hydrozinium

CO-ORDINATION CHEMISTRY 299 (2) Number of co-ordinate bonds Ligands are of six types depending upon the number of coordinate bonds: (a) Monodentate ligand Ligand, which can donate one pair of electrons to the metal ion. For example, Cl, NH3, H2O, SCN, NCS etc. (b) Bidentate ligand Ligand, which can donate two pairs of electrons to the metal ion. The complex where chelate rings are present is known as chelate complex. More is the chelate ring more will be stability of complex.

H2N(CH2)2NH2)
N

(Ethelene diamine) (c) (O-phenanthroline) Tridentate ligand Ligand which can donate three pairs of electrons to metal ion.
H2 ( C H2) 2N H ( C H ) 2 H 2 N 2 N M+ (Diethylene triamine)

(d)

Tetradentate ligand Ligand which can donate four pairs of electrons to metal ion.
H2 N(CH2) 2 NH (CH2) 2NH(CH2 )2NH2 M+ (Triethylnetetramine)

(e)

Pentadentate ligand Ligand which can donate five pairs of electrons to metal ion. Ethylene diamine triacetato ion.
O OCCH OCCH O (Ethylene diamine triacetato ion)
2 2

O N(CH2) 2N C H2 C O H

(f)

Hexadentate ligand Ligand, which can donate six pairs of electrons to metal ion.
O OCCH OCCH O
2 2

O N(CH2) 2N C H2 C O CHC O 2

O (Ethylene diamine tetracetato ion)

300 (3)

INORGANIC CHEMISTRY Spectrochemical series According to this, ligands are of two types: (a) Strong field ligand The ligand which will not follow Hund's rule and Aufbau principle is known as strong field ligand. For example, CN, CO, NCS, NO2, NH3, EtOH (ex). etc., (b) Weak field ligand The ligand which follows Hund's rule and Aufbau principle is known as weak field ligand. For example, Cl, Br, I, F, H2O, SCN etc. E.A.N. (EFFECTIVE ATOMIC NUMBER) He 2 Ne 10 Ar 18 Kr 36 Kr 36 Xe 54 Rn 86 EAN = Atomic number of central metal Oxidation state of central metal + 2 [Number of electron donated by ligands] For K4[Fe(CN)6], EAN = 26 2 + 12 = 36.

WERNER'SCOORDINATIONTHEORY Any complex salt has two types of valencies: (1) Primary valency is the charge on coordination sphere. (2) Secondary valency is number of coordinate bonds or coordination number. N M N L T R : O E CA U E (1) First rule is applicable for those complexes where the simple type of positive ion and complex types of negative ion are present.

(2)

(a) First preference goes to the positive ion, which is present in outer sphere. [Write name not number] (b) Second order goes to the ligands, if same type of ligands are there. So tri, tetra, penta and hexa terminology for 2, 3, 4, 5, 6 respectively. (c) Third order goes to the name of the metal. (If positive ion is present in outer sphere or co-ordinate sphere has negative charge, then you will write Greek name of metal atom and 'ate' suffix will be added.) (d) Last order goes to the oxidation state of metal in Roman numericals within the small bracket. Second rule is applicable for those complexes where complex type of positive ion and simple type of negative ion is present.
(2) (1) (4)
(3)

Hexaaquachromium(III) chloride

[Cr(H2 ) 6 C l 3 O ]

O. S.

(3)

Third rule is applicable for those complexes where more than one type of ligands are present. (a) If formula is given and we have to write the name, then charges does not matter there. We will write all these ligands according to alphabetical order. (b) If name is given and we have to write formula, then we will follow the following sequence for writing ligands after the metal alphabetically. Negative ligands Neutral ligands Positive ligands NH4 [Co Br Cl I NCS (NH3) (H2O)] (3) (4) (5) (6) (1) (2) Fourth rule is applicable to those complexs where the di, tri terminology creates controversy. To avoid that controversy we will use bis, tris, tetrakis, pentakis instead of di, tri, tetra and penta.

(4)

(NH2 (CH)2 NH ) 2 2 2 Bisethelenediamine

CO-ORDINATION CHEMISTRY (5) Fifth rule is applicable to those complexs where bridge ligands are present. B f r w i i g t eb i g l g n s e o e r t n , h r d e i a terms is used. d

301

Tetra aqua cobalt (III) -dihydroxotetraaquacobalt (III) sulphate or -dihydroxo octaaquadicobalt (III) sulphate or -dihydroxo bis (tetraaquacobalt(III)) sulphate

Tetraaquacobalt (III) -dihydroxotetraamminecobalt (III)sulphate

Tetraaquacobalt (III) -dihydroxoamminechromium (III) sulphate

(6)

Tetraaquacobalt (III) -amido--hydroxotetramine chromium (III) sulphate Sixth rule is applicable for those complex where the complex type of positive ion and complex type of negative ions are present. Tetraammine platinum (II) tetrachloroplatinate (II) Tetraammine dichloroplatinum (IV) tetrachloro platinate (II)

ISOMERISM
Two or more than two complexes having similar molecular weight or molecular formula but their structural arrangements are different. These forms are known as isomers and this phenomena is known as isomerism. (1) Ionization isomerism (2) Linkage isomerism (3) Hydration isomerism (4) Co-ordination isomerism (5) Co-ordination position isomerism (6) Polymerization Isomerism (7) Geometrical Isomerism (8) Optical isomerism Ionisation isomerism The isomerism which is due to change in position of ions is known as ionization isomerism. [Cr(H2O)5Cl]SO4 [Cr(H2O)5SO4]Cl

BaSO 4 white ppt.

AgCl
white ppt.

Linkage isomerism [Cr[H2O]5NO2]SO4 [Cr[H2O]5ONO]SO4 [Cr[H2O]5NCS] SO4 [Cr[H2O]5 SCN]SO4 The isomerism, which is due to different linkages of atoms to metal is known as linkage isomerism

302 INORGANIC CHEMISTRY Ambidentate ligand The ligands where two or more than two atoms can donate electron pairs but at a time only one can donate pair of electron. Such type of ligand is known as ambidentate ligand. The complex where ambidentate ligands are always present shows linkage isomerism. For example, NCS, SCN and NO2, ONO. Hydration isomerism Isomerism due to the change in position of water molecules in coordination sphere is known as hydration isomerism. [Cr(H2O)6]Cl3 Pale green [Cr(H2O)5Cl]Cl2.H2O Violet Penta aqua chloro chromium (III) chloride hydrate [Cr[H2O]4Cl2] Cl.2H2O Dark green Coordination isomerism Isomerism due to the change in coordination of ligands or metal is known as coordination isomerism. [Pt(NH3)4Cl2] [PtBr4] [Pt(NH3)4BrCl] [PtBr3Cl] [Pt(NH3)4Br2][PtBr2Cl2] Metal change [Co(H2O)6] [Cr(CN)6] [Cr(H2O)6][Co(CN)6] Co-ordination position isomerism

CO Cl2(HO) 2 Co 2 CO CO Cl(H2 O)3 Co CO

The isomerism due to change in position of ligands in the co-ordination spheres is known as co-ordination isomerism. Polymerization isomerism [Pt(NH3)2Cl2] Monomer [Pt(NH3)4][PtCl4] Dimer [Pt(NH3)3Cl]2[PtCl4] Trimer Geometrical isomerism The isomerism, which is due to change in geometry of molecule is known as geometrical isomerism. It is possible in square planar and octahedral complexs. It has two forms cis and trans. Types of geometrical isomerism in square planar complexes are: (i) [Ma2b 2] (ii) [Ma2bc] (iii) [Mabcd] (iv) [M(AB)2] M = Transition metal abcd = Monodentate ligand AB = Bidentate ligand

Co(H2 O)2 Cl2 SO4

Co Cl3H2O SO4

CO-ORDINATION CHEMISTRY Types of complex M(AA)2 M(AB)2 M(AA)cd M(AB)cd M(AA) a2 M(AB)a 2 M(AA)bc M(AB)bc Ma6 Ma5b Ma2b 4 Ma2bc Ma3b 3 Ma3b 2c Ma3bcd Ma2b 2c2 Ma2b 2cd Ma2bcde Mabcdef M(AA)a 4 M(AA)a 3b M(AA)a 2b 2 M(AA)abcd M(AA)2ab M(AA)2a2 M(AA)3 M(AB)3 Ma2b2 Coordination number 4 4 4 4 4 4 4 4 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 6 Number of isomers 1 2 1 2 1 1 1 2 1 1 2 2 2 3 4 5 6 9 15 1 2 3 6 2 2 1 2

303

The above compound is cisplatin used in cancer therapy. Ma2bc

M(AB)2
N
Gly

O
Gly

M
O O

Gly
N

M
O

Gly

Cis

Trans

304 GEOMETRICAL ISOMERISM IN OCTAHEDRAL COMPLEXES (i) Ma4b2

INORGANIC CHEMISTRY

(ii)

Ma3b3

(iii)

Ma2b2c2

(iv)

Mabcdef = 15 geometrical isomers and 30 optical isomers.

CO-ORDINATION CHEMISTRY (v) M(AA)2a2

305

(vi)

M(AA)2ab

(vii)

M(AA)a2b2

(viii) M(AB)3

OPTICAL ISOMERISM (a) A coordination compound, which can rotate the plane of polarised light is said to be optically active. (b) 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 such molecules are optical isomers. The optical isomers are pair of molecules, which are non-superimpossible mirror images of each other. (c) This is due to the absence of elements of symmetry in the complex. (d) Optical isomerism is expected in tetrahedral complexes of the type Mabcd. (e) These isomers are not ionisable due to their labile nature. (f) Example: Bis-benzoylacetonato- beryllium (II)
H3C HC C==O H5C6 CH 3 CO Be C==O C 6H5 H 5C 6 CO CH H 3C HC C==O CH3 CO Be O==C C 6 H5 OC CH

306 (g) (h) (a)

INORGANIC CHEMISTRY Optical isomerism is not present in square planar complexes on account of the presence of axis of symmetry. Optical isomerism is very common in octahedral complexes. [Ma2B2C2]n [Pt(py)2(NH3)2Cl2]2+

py Cl Pt Cl NH3
(b) [Mabcdef]

Py

2+

py py Pt Cl

2+

NH3

Cis-d-isomer
py py Pt Cl I
[M(AA)3]n

Cl NH3 Cis--isomer l Mirror [Pt(py)NH3NO 2ClBrI]

py

H3N

NO2

O2N Pt

py

NH3 d-isomer Mirror

H3N I l-isomer

Cl

(c)

[Co(en)3]3+

en en Co

3+

en

3+

Co en

en d-form

en Mirror l-form

en

Co

en en

(d)

[M(AA)2a2]n

'Meso' or optically inactive form [Co(en)2Cl2]+

en Cl Co Cl en Cis-d-form

3+ Cl Co Cl Mirror en Cis--form l

en

3+

Trans form of [M(AA)2a2]n does not show optical isomerism

CO-ORDINATION CHEMISTRY (e) [M(AA)2a2]n

307 (Co(en)2NH 3 Cl]2+

en Cl Co H3N en Cis-d-form
(f) [M(AB)3]

2+

en Cl Co NH3 en Mirror
(Cr(gly)3]

2+

Cis--form l

gly

gly

Cr

gly gly

Cr

gly Cis or trans-d-form Mirror

gly Cis or trans--form l

SOME MORE EXAMPLE ARE: [Cr(ox)3]3 ; [Fe(dipy)3]2+ ; [Cr(ox)2(H 2O) 2] ; [Pt(en)3]4+ (a) A complex is formed in solution by the stepwise addition of ligands to a metal ion. (b) This can be expressed as follows (c) [M] + [L] [ML] The stability constant K for this reaction is shown as K= (d) (e)

[ ML] [ M][ L]

This metal can again get a ligand. [ML] + [L] [ML2] The forthcoming stability constant is K1 K1 =

[ ML 2 ] [ ML ][ L]

(f) (g)

Its value is less than K. The higher the value of stability constant, stabler is the complex. The value of stability constant for some of the complexes are given below: Complex Stability constant [Cu(NH3)4]2+ 4.5 1011 2+ [Ag(NH3)2] 1.6 107 [Co(NH3)6]2+ 1.12 1011 2+ [Co(NH3)6] 5.0 1033 [AgCl2] 1.11 105 [AgBr2] 1.28 107 [Ag(CN)2] 1.0 1022 [Cu(CN)4]2 2.0 1027 3 [Fe(CN)6] 7.69 1043

308 INORGANIC CHEMISTRY STABILITYOFCOMPLEX More is charge radius ratio, more will be stability of complex. More is charge on central metal ion, more will be stability of complex. Smaller the size of central metal ion, more will be stability of complex. Mn 2+ Fe2+ Co 2+ Ni2+ Cu 2+ (Size decreases) CN and NH3 containing complexes are more stable than halogen containing complex because CN and NH3 are strong Lewis base. More is chelate rings, more will be stability of complex. More basic is the ligand, more stability of complex. CRYSTALFIELDTHEORY: This theory determines the effect of different electrostatic fields caused by the different geometries of complex and different basic strengths of ligands, on the energies of d-orbitals of the central metal ion. Salient Feature of Crystal field theory (1) The central metal cation is surrounded by ligands, which contain one or more lone pair of electrons. (2) The ionic ligands (e.g., F, Cl, CN etc.) are regarded as negative point charges (also called point charges) and the neutral ligands (e. g., H2O, NH3 etc.) are regarded as point dipoles or simply dipoles, i.e., according to this theory, neutral ligands are dipolar. If the ligand is neutral, the negative end of this ligand dipole is oriented towards the metal cation. (3) The interaction between the metal cation and the ligands is regarded as purely electrostatic, i.e., the metal-ligand bond is considered to be 100% ionic. CFT as applied to Octahedral Complexes: Splitting of d-orbitals in octahedral complexes

In case of free metal ion, all the five d-orbitals are degenerate, i.e., these have the same energy. Now let us consider an octahedral complex, [ML6]n+ in which the central metal cation, Mn+ is placed at the centre of the octahedron and is surrounded by six ligands, which reside at the six corners of the octahedron as shown in figure. The three axes viz., x-, y- and z-axes, which point along the corners have also been shown. Now suppose both the ligands on each of the three axes are allowed to approach towards the metal cation, M n+ from both the ends of the axes. In this process, the electrons in d-orbitals of the metal cation are repelled by negative point charge or by the negative end of the dipole of the ligands. (Remember CFT regards the ionic ligand as negative point charges and neutral ligands as dipoles). This repulsion will raise the energy of all the five d-orbitals. If all the ligands approaching the central cation are at an equal distance from each of the d-orbitals (i.e., the ligand field is spherically symmetrical), the energy of each of five d-orbitals will be raised by the same amount i.e., all the d-orbitals will still remain degenerate, although they will now have higher energy than before. This is only a hypothetical situation. Since the lobes of the two e g orbitals (i.e. dz2 and d x2y2 orbitals) lie directly in the path of the approaching ligands, the electrons in these orbitals experience greater force of repulsion than those in three t 2g orbitals (i.e., d xy, d yz and d zx orbitals) whose lobes are directed in space between the path of the approaching ligands i.e., the energy of eg orbitals is increased while that of t2g is decreased (Remember: Greater is the repulsion, greater the increase in energy). Thus, we find that under the influence of approaching ligands, the five d-orbitals, which were originally degenerate in the free metallic cation are not split (or resolved) into two levels viz. t 2g level, which is triply degenerate and is of lower energy, and eg level, which is doubly degenerate and is of higher energy (See figure) . In other words, the degeneracy of the five d-orbitals is removed under the influence of the ligands. The separation of five d-orbitals of the metal ion into two sets having different energies is called crystal field splitting or energy level splitting. This concept of crystal field splitting makes the basis of CFT.

CO-ORDINATION CHEMISTRY 309 The energy gap between t 2g and eg sets is denoted by 0 or 10Dq where o in 0 indicates an octahedral arrangement of the ligands around the central metal cation. This energy difference arises because of the difference in electrostatic field exerted by the ligands on t2g and eg sets of orbitals of the central metal cation. 0 or 10Dq is called crystal field splitting energy. With the help of simple geometry, it can be shown that the energy of t 2g orbitals in 0.4 0 (= 4Dq) less than that of hypothetical degenerate d-orbitals (No splitting state shown by dotted line in figure) and, hence, that of eg orbitals in 0.6 0 (= 6Dq) above that of the hypothetical degenerated d-orbitals. Thus, we find that t 2g set loses an energy equal to 0.4 0 (= 4Dq) while eg set gains an energy equal to 0.6 0 (= 6Dq). In figure, the loss and gain in energies of t 2g and eg orbitals is shown by negative and positive signs respectively.
eg
z 2 x2 y 2

Energy increasing

xy

yz zx z2 x2y 2

+0.60=+6Dq 0 or 10Dq -0.4 0=-4Dq xy yz zx

xy yz zx z 2 x2 y 2

t2g

eg
Hypothetical degenerate d-orbitals at a higher energy level

t2g
Splitting of d-orbitals under the influence of six ligands in octahedral complex

Five degenerate d-orbital on the central metal cation which are free from any ligand field

Crystal field splitting of d-orbitals in octahedral complex

Filling up of t2g and eg Orbitals with Electrons in Octahedral Complexes : High spin and Low spin Octahedral Complexes For octahedral complexes containing weak ligands (i.e., weak field complexes), the energy difference, 0 between t2g and eg sets is relatively small and hence the energy of all the five d-orbitals is supposed to be the same. Consequently, the filling of t 2g and eg orbitals takes place according to Hund's rule, i.e., electrons pair up only when each of the five d-orbitals is at least singly filled. Thus, in case of weak field complexes the distribution of d 1 to d 10 electrons in t 2g and eg orbitals takes place as d 1 = t 2g1eg0 (n = 1, S = n/2 = 1/2) ; d 2 = t2g2eg0 (n = 2, S = 1) ; d 3 = t 2g3eg0 (n = 3, S = 3/2); d 4 = t 2g3eg1 (n = 4, S = 2) ; d 5 = t 2g3eg2 (n = 5, S = 5/2); d 6 = t 2g4eg2 (n = 4, S = 2) ; d 7 = t2g5eg2 (n = 3, S = 3/2) ; d 8 = t 2g6eg2 (n = 2, S = 1) ; d 9 = t 2g6eg3 (n = 1, S = 1/2); d 10 = t 2g6eg4 (n = 0, S = 0). Here n = number of unpaired electrons and S = resultant spin which is equal to n/2. For octahedral complexes containing strong ligands (i.e., strong field complexes) all the three d-orbitals of low energy t 2g set are filled up first and then the two d-orbitals of high energy eg set are filled. Thus, in this case, the distribution of d1 to 10 electrons in t 2g and eg orbitals takes places as: d 1 = t 2g1eg0 (n = 1 S = 1/2) ; d 2 = t 2g2eg0 (n = 2, S = 1/2); d 3 = t 2g3eg0 (n = 3, S = 3/2); d 4 = t 2g4eg0 (n = 2, S = 1); d 5 = t 2g5eg0 (n = 1, S = 1/2) ; d 6 = t 2g6eg0 (n = 0 , S = 0) ; d 7 = t 2g6eg1 (n = 1, S = 1/2); d 8 = t 2g6eg2 (n = 2, S = 1) ; d 9 = t 2g6eg3 (n = 1, S = 1/2) ; d 10 = t 2g6eg4 (n = 4, S = 0). It may be seen that the weak field octahedral complexes of d 4, d 5, d 6 and d 7 ions have greater number of electron (S) than those of (same ions) strong field complexes. It is for this reason that weak field complexes of d 4, d 5, d 6 and d 7 ions are also called high spin or spin free complexes. Similarly, strong field complexes are also called low spin or spin paired complexes. Recall that VBT has called high spin complexes as ionic (Pauling) or outer orbital (Huggin) complexes while the same theory has called low spin complexes as covalent or inner orbital complexes. Crystal Field Stabilization, Energies of Octahedral Complexes We have seen that, according to CFT, under the influence of the six ligands approaching towards the central metal ion during the formation of an octahedral complex, the d-orbitals of the central metal ion split into two sets of orbital viz. lower energy triplet (or trio) t2g and higher energy doublet (or pair), eg. The t 2g set of orbitals is triply degenerate while eg set is doubly degenerate. The energy gap between these two sets is equal to 0 (or 10Dq). The energy of t 2g set is lowered by 2/5 0 (= 0.4 0) or 4Dq while that of eg set is raised by 3/5 0 = (0.6 0) or 6Dq relative to the energy of hypothetical degenerate d-orbitals. Thus, each electron occupying t2g orbitals decreases the energy of d-orbitals by 0.4 0 (= 4Dq) while that going into e g orbitals increases its energy by +0.6 0 (= +6Dq). + signs indicate respectively the decrease and increase in the energy of d-orbitals caused by their splitting under the influence of six. Now let us consider a dx ion containing t 2gpegq configuration in which p is the number of electrons in t 2g set and q is the number of electrons in eg set and x = p + q. Quite obviously:

310 Change in energy (in terms of 0) for t 2gpegq configuration = Loss in energy due to p electrons in t 2g set + Gain in energy due to q electrons in eg set = 0.4 0 p + 0.6 0 q = [0.4 p + 0.5 q] 0 (i) Now since 0 = 10Dq, the above expression can also be written as Change in energy (in terms of Dq) for t 2gpegq configuration = [0.4p + 0.6 q] 10Dq = [ 4p + 6q] Dq (ii) CFT as applied to Tetrahedral complexes: Splitting of d-orbitals in Tetrahedral Complexes z

INORGANIC CHEMISTRY

L L Mn+ y

L
A tetrahedron is placed in a cube. The centre of the cube is at the centre of the tetrahedron at which is placed central metallic cation, Mn+. Four corners of the cube are at the four corners of the tetrahedron at which are placed the four negative ligands, which have been shown by circles with negative signs. In order to understand the splitting of d-orbitals in tetrahedral complexes, a tetrahedron should be pictured as being placed in a cube as represented in figure. It may be seen from the figure that the four negative ligands (represented by circles with negative signs) placed at the four corners of the tetrahedron are located at the four corners of the cube. Thus, these four ligands are lying between the three axes viz., x, y and z axes, which pass through the centre of the cube. Now the lobes of t 2 orbitals (d xy, d yz and d zx) are lying between the axes, i.e., are lying directly in the path of the ligands. These orbitals will experience greater force of repulsion from the ligands than those of e orbitals (d z2 and d x2y2) whose lobes are lying along the axes, i.e. are lying in space between the ligands. Thus, the energy of t 2 orbitals will be increased while that of e orbitals will be decreased. Consequently, the d-orbitals are again split into two sets as shown in figure. From which it may be seen that the order of energy of t 2 and e sets is the reverse of that seen for t 2g and eg sets in octahedral complexes.
t2 xy yz zx +0.40
No splitting state

Energy increasing

xy

yz

zx z2 x 2y 2

t = 0.45 -0.60

z2 x 2y2 xy yz zx z2 x2 y2

(e) t2 e
Hypothetical degenerate d-orbitals at a higher energy level Splitting of d-orbitals under the influence of four ligands in a tetrahedral complex Five degenerate d-orbitals on the central metal cation

Crystal field splitting of d-orbitals in tetrahedral complex. The energy difference between t 2 and e sets tetrahedral complex is represented as t . It has been shown that t < 0 , the cause of which is that t 2 orbitals, although now closest to the ligands, do not point directly at the ligands, i.e., in an octahedral complex there is a ligand along each axis and in a tetrahedral complex no ligand lies directly along any axis. For this reason and also because there are only four ligands in the tetrahedral complex, while in an octahedral complex there are six ligands, the tetrahedral orbital splitting, t is less than 0, for the same metal and ligands and these are at same internuclear distances. It has also been shown that t = 0.45 0. Thus, the energy level of the t 2 set is raised by 0.4 t = 0.18 0 while that of e set is lowered by 0.6 t = 0.27 0. The relational t = 0.45 0 also shows that, other things being equal, the crystal field splitting in a tetrahedral complex will be about half the magnitude of that in octahedral complex. Since t is relatively small orbital splitting, spin-pairing in tetrahedral complexes in rather unlikely. Since t< 0, crystal field splitting favour the formation of octahedral complexes. Note: The subscript g is not used for the splitting of d-orbitals in tetrahedral complexes because a tetrahedron has no centre of symmetry. The symbol g is used for the ligands fields, which have centre of symmetry. (So instead of t2g and eg we can write t2 and e).

CO-ORDINATION CHEMISTRY 311 Splitting of d-orbitals in tetragonally distorted octahedral and square planar complexes Before considering the splitting of d-orbitals of the central metal cation in these complexes, we should understand how tetragonally distorted octahedral and square planar geometries are obtained from regular octahedral geometry. Consider a regular (symmetrical) octahedral complex, [M(Lb)4 (La)2] in which La are two trans-ligands (i.e., La are the ligands lying along the z-axis) and Lb are the basal ligands lying in xy plane. In this complex, all the bond axis distances (four M Lb and two M La distances) are equal [See figure]. Now if two La ligands are moved slightly away from the central metal cation, then each of the four co-planar MLb distances, the symmetrical shape of octahedral complex becomes tetragonally distorted octahedral shape [See figure]. Now if the two La ligands are completelyremoved away from z-axis, the tetragonally distorted octahedral shape become square planar [See figure (c)].
La La

La

Lb

Lb

Lb

Lb
Both La ligands are completley removed

Lb

M
Lb

Both La ligands are moved slightly away from M

M
Lb Lb

M
Lb Lb

Lb

Regular octahedral geometry (M L a = M Lb)

La

Tetragonally distorted octahedral geometry (M L a = M Lb )

La

Square planar geometry

(a)

(b)

Now consider the splitting of d-orbitals in tetragonally distorted octahedral and square planar complexes. We start with the spliting of d-orbitals in octahedral complexes. We have already seen that in octahedral complexes, the energy of dxy, dyz and dzx orbitals (t 2g orbitals) is decreased while that of d
x2

and d

x2 y2

orbitals (e g) orbitals is increased figure (a). Now in tetragonally distorted

octahedral complex, since the distance of the trans-ligands (La ligands) is increased from the central metal ion by removing them away along the z-axis, d-orbitals along the z-axis (i.e., d
z2

orbital), in xz (i.e., d xz) and yz (i.e., d yz) planes experience less repulsion from the
x2 y2

ligands as they do in the octahedral complex while the d-orbitals in xy plane (i.e., d xy and d

orbitals) experience more repulsion

x2 y2

than they do in the octahedral complex. Consequently, the energy of d xz, d yz and d zx orbitals decrease while that of d

and d xy

orbitals increase [See figure (b)]. Note that d yz and d xz orbitals will remain degenerate as they are in the octahedral complex. In square planar geometry, the energies of d
z2

, d y and d zx orbitals again fall down while those of d

x2 y2

and d xy orbitals rise up [see figure (c)]

Energy increasing

(eg ) 2 z2 xy 2
2 xy yz zx z2 xy 2

x 2y2 x 2y2 xy

+0.6 0=+6Dq

0 or 10Dq

z2 xy z2

t2g

eg

sp
3

-0.40=-4Dq

xy yz

zx yz zx yz zx

(t 2g )

Five degenerate d-orbitals on the central metal cation which are free from any ligand

Splitting of d-orbitals in octahedral geometry

Splitting of d-orbitals in tetragonally distorted octahedral geometry

Splitting of d-orbitals in square planar geometry

Crystal field splitting of d-orbitals in octahedral, tetragonally distorted octahedral and square planar complexes

312 INORGANIC CHEMISTRY The crystal field splitting energy in square planar complex is denoted by sp and is given by: sp = E(d x2 y2) E(d xz, dyz) = x + 2 + 3 [See fig.] The value of sp has been found larger than 0 (sp = 1.30) because of the reason that d xz and d yz orbitals interact with only two ligands in the square planar complexes, while in octahedral complexes the interaction takes place only with four ligands. Applications of Crystal field Theory: The following properties of transition metal complexes can well be explained on the basis of CFT. 1. Colour of transition metal complexes It has been seen that the solution of transition metal complexes formed by metal cations having no unpaired electrons in d-orbitals (i.e., having completely filled or vacant d-orbitals) are colourless while the solution of transition metal complexes given by transition metal cations having one or more unpaired electrons in d-orbitals are coloured. The colour of transition metal complexes having unpaired electrons in d-orbitals can well be explained by considering the example of [Ti(H2O)6]3+ ion, which is an octahedral complex and has purple colour. Now when white light is allowed to fall on this complex ion, the ion absorbs radiation from the white light (i.e., visible spectrum). The maximum absorption takes place at a wavelength of 5000. The absorbed light of this wavelength is green and the transmitted light corresponding to this absorbed light is purple, which is the colour of [Ti(H2O)6]3+ solution. The cause of colour can also be explained on the basis of CFT as follows: We know that Ti3+ ion has the configuration t 2g1eg0. Now when white light is allowed to fall on [Ti(H2O)5]3+ ion, the unpaired electrons present in t 2g set of orbitals move from lower energy t 2g set to higher energy eg set, since the energy of the radiation absorbed by unpaired t 2g electron is the same as the energy difference between t 2g and eg sets (see figure). This type of electronic transition from t 2g to eg level is called dd or ligand-field transition, which is the cause of the colour of [Ti(H2O)6]3+ ion.

e g

e'g

Light absorbed a = E = 57 calories/mole = 5000 and E = 57 calories/mole

t'2g

Ground state of [Ti(H 2O)6]3+ (t2g1eg0) Excited state of [Ti(H 2O)6]3+ (t2g0eg1)

t2g

Absorption of light by [Ti(H2O )5]3+ ion involving a shift of an electron from 2tg level to e g level. This transition [t2g1e g0 t2g0e g1] gives the [Ti(H2O)6]3+ ion its purple colour.

2 .

Magnetic moment value of complex compounds CFT can be used to find out the number of unpaired electrons (n) in a given octahedral complex. The substitution of n value in the spin only formula, =

n (n + 2) gives the value of magnetic moment, of the given complex compound. From the

knowledge of n value of valence state of the central metal cation and the nature of bonding in the complex (i.e., whether the complex is high spin or low spin) can be known.

EXAMPLES
1. [Ni(CN)4]2 Ni +2 configuration

3d
Ni Ni 2+ [Ni(CN)4]2

4s

4p

CN CN CN CN d s p2 hybrid used [Ni(CN)4]2 is square planar and diamagnetic. [NiCl4]2 , on the other hand, is paramagnetic and has tetrahedral 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:

CO-ORDINATION CHEMISTRY [NiCl4]2 is paramagnetic as there are two unpaired electrons.

313

3d
Ni Ni 2+

4s

4p

[Ni(Cl)4]2

Cl
2. [Cr(H2O) 6] Cl3 [Cr(H2O) 5Cl]Cl2.H 2O [Cr(H2O) 4Cl2]Cl.(H2O) 2 CuSO4 + KF CuSO4 + KCl Violet Green Dark green colour CuF2 + K2SO 4 Green ppt. CuCl2 + K2SO 4 Green solution

Cl Cl Cl s p 3 hybrid used

3.

4.

K3[Cu(CN) 4] CuSO4 + KCN Cu(CN)2 Cu(CN)2+ (CN)2 2 + ions so with H S it forms K S but not Cu S due to lack of Cu 2+ ions. Because it produces K 2 2 2
(i) [Fe(CN)6]4 Fe26 Fe +2 3d 6

5.

d2sp3
(Due to strong field ligand) (ii) [FeF6]3 Fe +3 3d 5

s p3d2
(iii) [Co(OX)3]3 (iv) Co27, 3d74s 2 Co +3 3d 5

sp3d2
(v) [CoF6]3 , sp3d 2 Co +3 3d 5

sp3d2

314 6.

INORGANIC CHEMISTRY Magnetic criteria of bond K4[Fe(CN)6] Fe 3d6 Fe +2 3d 6

d2sp3
This is diamagnetic in nature. K3[Fe(CN)6]

d2sp3
Fe +3 3d 5 This is paramagnetic in nature.

ORGANOMETALLICS
The compound in which the organic group is directly attached with metal atom is known as organic nonmetallic compound and a carbon-metal bond should be present there. (1) Grignard reagent, RMgX C2H5ONa not an organometallic compound. (2) Zigler Natta salt Mixture of TiCl4 + R3Al. It is a heterogenous catalyst and acts as catalyst for rubber polymerise atom reaction. (3) Wilkonson's catalyst [{(Ph)3P}3Rh]Cl It is homogenous catalyst and acts as catalyst for hydrogenation of alkanes. (4) Ziese's salt

(5)

2 potassium trichloro ethylene platinated (II) Ferrocene

(6)

5 -biscyclopentadienyl iron (II) 6 Bisbenzene chromium (0)

Ti+4

1 biscyclopentadienyl 5 bicyclopentadienyl titanium (IV)

CO-ORDINATION CHEMISTRY (7) Dimer of trimethyl aluminium

315

(8)

Hybridisation in Al is sp3. [Mn(CO)6] [Ni(CO)4]

sp3 hybridization
Ni (28)

C O

C O

C O

C O

Ni electronic configuration [Ar]

4s 23d 8

O C Ni C O O O (Tetrahedral) C C
M C O M M C O M C O+

Bonding in metal and carbonyl

[Mn2(CO)10]

d2sp3hybridization

C O

C O

C O

C O

C O

d2sp3hybridization

C O

C O

C O

C O

C O

316 Fe2(CO)9

INORGANIC CHEMISTRY

d3sp3hybridization

C
C=O

C O

C O

O=C

C=O

d3sp3hybridization

C O

C O

C O