Lecture-28

Introduction to Coordination Compounds

ADDITION COMPOUNDS When stoichiometric amounts of two or more stable compounds join together two types of addition compounds can be formed. (i) Double salts (ii) Co-ordination Compounds Examples: (i) Double Salts:
(i) KCl + MgCl2 + 6H2O KCl.MgCl2.6H20 (carnallite) K2SO4.Al2(SO4)3.24 H2O

(ii) K2SO4 + Al2(SO4)3+24 H2O

(potassium alum) A double salt looses its identity in solution

(ii) Co-ordination Compounds: (a) CuSO4 + 4NH3 + 2H2O CuSO4.4NH3.2H2O [tetrammine copper (II) sulphate dihydrate) Exists as [Cu(H2O)2(NH3)4]2+ (Deep Blue) Cu2+ exists as [Cu(H2O)6]2+ in aqueous soln and in hydrated crystalline salts (Pale Blue) (b) Fe(CN)2 + 4KCN Fe(CN)2. 4KCN

K4[Fe(CN)6] Potassium ferrocyanide [Fe(CN)6]4- is stable in solution.

Alfred Werner : Nobel Prize 1913 Werners Co-ordination Theory-1893

Wernerr Work
Synthesized many compounds like CoCl3.6NH3; CoCl3.5NH3 ; CoCl3.4NH3 CoCl3.6NH3 = [Co(NH3)6]Cl3 Without any modern analytical tools as IR, NMR, X-ray, He predicted primary, secondary valencies The structure of [Co(NH3)6]3+ to be octahedral

Primary valency: Non-directional; Equivalent to the number of charges on the complex ion. Applicable to simple salts and complex ions. Example: CoCl2 Primary Valency = 2 Secondary valency: Directional; Equals to the no. of Ligands coordinated to the metal. Also called co-ordination number For [Co(NH3)6]Cl3 Prim. Val =3; Sec.Val=6

Treatment of some Cobalt complexes with excess AgNO3

CoCl3.6NH3 CoCl3.5NH3 CoCl3.4NH3 3AgCl [Co(NH3)6]3+ 3Cl,

2AgCl [Co(NH3)5Cl]2+ 2ClAgCl [Co(NH3)4Cl2]+ Cl-

6-Coordination 1.Octadedron
The octahedron is one of the five REGULAR POLYHEDRA, having 8 identical equilateral-triangle faces. 6 vertices, each vertex is surrounded by four faces. 12 edges The sum of the face angles at each vertex is 240.

Other Geometries (for 6 Coordination)

2. Planar Hexagon and 3.Trigonal Prism

Number of isomers
Complex Observed Octahedron MX6 MX5Y MX4Y2 MX3Y3 1 1 2 2 1 1 2 2 Planar Hex. 1 1 3 3 Tri. Prism 1 1 3 3

Solid CoCl36NH3 CoCl35NH3 CoCl34NH3 CoCl34NH3

Color Yellow

Ionized Cl3

Formula

[Co(NH3)6]Cl3 [Co(NH3)5Cl]Cl2 trans[Co(NH3)4Cl2]Cl cis[Co(NH3)4Cl2]Cl

Purple

Green

Violet

Isomers
Octahedral: disubstituted tri substituted Planar hexagon: di tri Exercise: Trigonal Prism cis, trans facial (fac), meridinal (mer) ortho, meta, para 123, 124, 135

4 coordination
1.Tetrahedral and 2.square planar [Pt(NH3)2Cl2], Pd(NH3)2Cl2] 1 possible isomer 2 possible isomers Tetrahedron Square planar

He was able to isolate 2 isomers confirming Square planar structure.

Other Methods of Study (i) Conductivity

Cryoscopy Number of Charges.

freezing point depression no: of particles.

For Co(NO2)3.KNO2. 2NH3 2 particles and 2 charges K+ [Co(NH3)2 (NO2)4]-

Conductivities of Salts and Complexes (Measured in 0.001M Concentration)

(total of 2 charges) 112.0 ohm-1cm2mol-1 (ii) CaCl2 Ca2+ 2Cl- (total of 4 charges) 260.8 ohm-1cm2mol-1 (iii) CoCl3.5NH3 (total of 4 charges) 261.3 ohm-1cm2mol-1 (iv) LaCl3 La3+ 3Cl- (total of 6 charges) 393.0 ohm1cm2mol-1 (v) CoCl3.6NH3 (total of 6 charges) 431.0 ohm-1cm2mol-1 (i) LiCl Li+ Cl-

Conductivity Measurement together with Cryoscopic Measurement

Formula Cryoscopic Measurement 4 particles 3 particles 2 particles 1 particle Molar Conductivity 6 charges 4 charges 2 charges 0 charge 6 charges Structure

(i) CoCl3.6NH3 (ii) CoCl3.5NH3 (iii) CoCl3.4NH3 (iv) CoCl3.3NH3

[Co(NH3)6]3+3Cl[Co(NH3)5Cl]2+2Cl[Co(NH3)4Cl2]+Cl[Co(NH3)3Cl3] 3K+[Co(NO2)6]3-

(v) Co(NO2)3.3KNO2 4 particles

Other methods of Study

(ii) Dipole moment: cis and trans isomers of [Pt(NH3)2Cl2]; trans isomer has no electric dipole moment. (iii) Magnetic moment NiII(NH3)4(NO3)2.2H2O two structures possible. (a) [NiII(NH3)4]2+.2H2O Sq. Planar, No unpaired electron (b) [NiII(H2O)2(NH3)4]2+ Octahedral, Two unpaired electrons (iv)Electronic Spectra: Provide informations on the energy of the orbitals, shape of the complex, whether regular or distorted etc.

Effective Atomic Number

[Cu(CN)4]3Atomic Number of Cu: 29 Charge X-4 = -3 X= +1= electrons lost 4 ligands = 8 electrons gained EAN = 29-1+8 = 36 (Atomic No. of Kr) Gives stable compound. Violated in many places

Effective Atomic Numbers of Some Metals in Complexes

Atom
Cr Fe Fe Co Ni Cu Pd Pt Fe Ni Pd Pt

At. No. Complex

24 26 26 27 28 29 46 78 26 28 46 78 [Cr(CO)6] [Fe(CN)6]4[Fe(CO)5] [Co(NH3)6]3+ [Ni(CO)4] [Cu(CN)4]3[Pd(NH3)6]4+ [PtCl6]2[Fe(CN)6]3[Ni(NH3)6]2+ [PdCl4]2[Pt(NH3)4]2+

Elec. Lost
0 2 0 3 0 1 4 4 3 2 2 2

Elec. Gained
12 12 10 12 8 8 12 12 12 12 8 8

EAN
36 (Kr) 36 (Kr) 36 (Kr) 36 (Kr) 36 (Kr) 36 (Kr) 54 (Xe) 86(Rn) 35 38 52 84