1. INTRODUCTIONCrystal field theory Proposed by Bethe and van Vleck. Used in 195oIt defines the bonding in ionic crystals due to which this theory is known as crystal field theory.Orgel used the concept of crystal field theory to define nature of bonding between ligands and metals.This theory involves an electrostatic approach to the bonding in complexes.

2. Werners theory Alfred Werner 1893 Nobel prize in 1913 According to this theoryComplex metal shows two types of valency which are as follows:(a) Primary valencies (b) Secondary valencies 3. Primary valency 1. 2. 3. 4.It is equal to the oxidation state of central metal atom. It is non directional in nature . It can not define the geometry. Primary valency exhibiting species can or can not retain their individual identity.Secondary valency1. It is equal to the co-ordination number of central metal atom. 2. Secondary valency exhibiting species are directional in nature. 3. Secondary valency of central metal atom is responsible for geometry of complexes. 4. Those species which exhibit the secondary valency in the complex can not retain their individual identity. 4. Example- Complex =[Co(NH)6 ]Cl3 1.Primary valency = +3 2.Secondary valency = 6 (C.N) 3.Primary valency is exhibited by 6NH ligand. 4.Secondary valency is exhibited by 3Cl ligand. 5.Geometry = octahedral. 5. Limitation of Werners theory 1- This theory was failed to define the geometry in the case of four secondary valency. 2- This theory was failed to define the nature of bonding between the ligand and central metal atom. To overcome this limitation a new theory was proposed which is VALENCE BOND THEORY. 6. Valence bond theory Proposed by Pauling and Slater in 193o. Hybridization based theory. Define covalent nature of bonding between metal and ligand. Define properties of complexes. Limitation of Valence bond theory 1. VBT was failed to define the color of the various complexes. 2. VBT can not define the strength of the ligands. 3. According to VBT four co-ordinated complex of Cu in +2 oxidation state being always square planar. Which is not explained by VBT. 4. VBT was failed to define the orbital contribution in the magnetic moment value of the complexes. 7. Postulates of crystal field theory 1- Central metal atom is surrounded by ligands to form complex. 2- Type of ligand Point charge Point dipole 3-The bonding between metal cation and ligands arises due to electrostatic interaction . Thus the bond between metal and ligand is purely ionic.4-The interaction between electron of the metal cation and those of the ligand is entirely repulsive. These repulsive forces are responsible for the splitting of the d orbital of the metal cation. 5- The d orbital which are degenerate in free metal ion have their degeneracy destroyed by the approach of ligand during the formation of complex. 8. CRYSTAL FIELD THEORY FOR OCTADERAL COMPLEXCrystal field theory for octahedral complex can be explained in following five step which are as follows.Step1- SHAPE OF d ORBITAL- 9. 1. STEP 2Orientation of ligand around central metal atom 10. STEP 3-CRYSTAL FIELD SPLITTING OF THE OCTADERAL COMPLEXeg t2gDegenerate 5d orbitalMetal ion and ligand at infinite distance awayHypothetical Degenerate 5d orbital3d orbital are split into Two sets 11. STEP 4Arrangement of d configuration of central metal ion in t2g and eg set of orbitalTo define the arrangement of d of central metal atom in octahedral complex at first we have to define spectrochemical series. SPECTROCHEMICAL SERIES- Arrangement of the ligand in order of their increasing splitting power to the d configuration is known as spectrochemical series. Which is given below. 12. In case of strong ligandEither weak or strong ligandIn case of weak ligand 13. Either strong or weak ligand 14. STEP 5-Crystal Field Splitting Energy (CFSE) In Octahedral field, configuration is: t2gpegq Net energy of the configuration relative to the average energy of the orbital's is:= (-0.4p + 0.6q)O BEYOND d3In strong field O P, => t2g4 eg o In weak field: O P, => t2g3eg1 P - paring energy 15. CFT FOR TETRAHEDRAL COMPLEX CFT for tetrahedral complex can also be explained in five steps which are as follows.STEP 1- Shape of 5d orbital1. Axial or eg set of the orbital- Out of 5d orbital two orbital mm and being present over axis are known as axial set of orbital.2. Non-axial or t2g set of the orbital- Out of 5d orbital remaining three orbital being present between the axis are known as non-axial set of orbital. 16. STEP 2- ORIENTATION OF LIGAND AROUND CENTRAL METAL ION IN TETRAHEDRAL COMPLEXOR 17. STEP 3-CRYSTAL FIELD SPLITTING FOR TETRAHEDRAL COMPLEX 18. STEP 4- Arrangement of electron in d orbital in tetrahedral complexEither weak or strong ligand it will be of high spin. 19. SETP 5 Crystal field energy difference in tetrahedral complex CFSE value for tetrahedral complex = (-.6q+.4p)twhere, q = the number of electron in eg set of orbital , p = number of electron in t2g set of orbital. 20. CFT FOR SQUARE PLANAR COMPLEX 1. In the octahedral complex all six metal ligand bond being identical .If the ligand related with the z- axis are slightly removed outward then their occur the formation of distorted octahedral complex. 2. In second step ligand related with z-axis are completely removed outward then their occur the formation of square planer complex . 21. Factor affecting the value of 1. Oxidation state of metal ion-2. Nature of ligandStrong ligand = high value Weak ligand = low value3. Geometry- value is also affected by geometry of complex. 22. Applications of CFT Determination of CFSE value With the help of CFT we can determine the CFSE value of the octahedral and tetrahedral complex by following formula.CFSE value for tetrahedral complex = (-.6q+.4p)+ nP CFSE value for octahedral complex = (-.4p+.6q) + nPn = no of paired electron P = pairing energy p and q are no. of electron in eg and t2g set of orbital respectively 23. 3. Geometry- value is also affected by geometry of complex.Application of CFT Determination of CFSE VALUE with the help of CFT we can determine the CFSE value of the octahedral and tetrahedral complex by following CFSE value for formula. tetrahedral complex = (.6q+.4p)+ nP CFSE value for octahedral complex = (-.4p+.6q) + nP n = no of paired electron P = pairing energy p and q are no. of electron in eg and t2g set of orbital respectively 24. Use of CFSE value Spinel structure determination = All the mix oxide with the general formula AB2O4 are known as spinel from the name of mineral spinel MgAl2O4 in which both the A2+ and B3+ cation be similar or different. 25. Example 1- Mn3O4 ( O is a weak field ligand)CFSE under weak field octahedral condition0-.6CFSE under weak field tetrahedral condition0-.18Will occupy octahedral void since its CFSE value is more negative. and mnm will occupy tetrahedral void. Therefore it is a normal spinel. Example2-CFSE under weak field octahedral condition-.40CFSE under weak field tetrahedral condition-.270It is a inverse spinel. 26. Color of the complexes 1. 2. 3.Absorb all EMR black Transmitted all EMR - White Absorb radiation of visible range colored Complexes shows color because of the phenomena of d-d transition. d-d transition phenomena- 27. Color can change depending on the following factor: 1.Metal charge( size of metal) 2. Ligand strength 28. Magnetic behavior If d orbital contain no unpaired electron = Diamagnetic If d orbital contains unpaired electron = paramagnetic = {n(n+2)}1/2 BMagnetic moment = Where n is no. of unpaired electron WhereB = eh/4me = 9.274 10-24 J T-1 29. Ionic radii of transition metal ion= for given oxidation state ionic radii are regularly decreases in transition metal complex. 30. JAHN TELLER EFECT If both the eg orbital are symmetrically filled- all ligand repel equally. Result = regular octahedron If asymmetrically filled - some ligand are repel more than other. Result = Distorted octahedron 31. Consider eg configuration 32. Consider eg configuration =Z- OUT DISTORTION- 33. Published in 1937 . This theorem state that there can not be unequal occupation of orbital with identical energy. To avoid such unequal occupation, the molecule distort so that these orbital are no longer degenerate. The effect of John Teller is best documented for Cu() 34. Limitation of CFT 1. This theory does not consider the splitting of the orbital other than d orbital. 2. The order of ligand in the spectrochemical series can not be explained solely on electrostatic ground.3.CFT was failed to explain co-valency in certain metal ligand bond.4. CFT can not define the orbital contribution in magnetic moment of complex.CFT = Crystal field theory 35. REFRENCES Gary L. Miessler and Donald A. Tarr V Ramalingam Alen G Sharpe www.wikipedia/ crystal field theory 36. THANK YOU