John_Teller effect in octahedral complexs.pptx

John Teller Effect

1. JOHN TELLER EFFECT IN OCTAHEDRAL COMPLEX PRESENTED BY Ashwini Vishwakarma M.Sc. Chemistry 1 st Sem UIT, BU BHOPAL

2. JOHN TELLER DISTORTION The John-Teller effect is a geometric distortion of a non-linear molecular system that reduces its symmetry and energy. This distortion is typically observed among octahedral complexes where the two axial bonds can be shorter or longer than those of the equatorial bonds. This effect can also be observed in tetrahedral compounds. This effect is dependent on the electronic state of the system. We can understand this effect in the context of octahedral metal complexes by considering d-electron configurations in which the  e g  orbital set contains  one or three electrons . The most common of these are high spin d 4 , low spin d 7  and d 9  (e.g., Cu 2+ )

3. For a given octahedral complex, the five d atomic orbitals are split into two degenerate sets when constructing a molecular orbital diagram. These are represented by the sets symmetry labels: t 2 g (dxz, dyz, dxy) and eg (dz 2  and dx 2 −y 2 ). When a molecule possesses a degenerate electronic ground state, it will distort to remove the degeneracy and form a lower energy (and by consequence, lower symmetry) system. The octahedral complex will either elongate or compress

4. ELONGATION Elongation Jahn-Teller distortions occur when the degeneracy is broken by the stabilization (lowering in energy) of the d orbitals with a  z component, while the orbitals without a  z  component are destabilized (higher in energy). This is due to the dxy and dx 2 −y 2  orbitals having greater overlap with the ligand orbitals, resulting in the orbitals being higher in energy. Since the dx 2 −y 2  orbital is  antibonding , it is expected to increase in energy due to elongation. The dxy orbital is still nonbonding, but is destabilized due to the interactions. Jahn-Teller elongations are well-documented for copper(II) octahedral compounds.

5. COMPRESSION Compression Jahn-Teller distortions occur when the degeneracy is broken by the stabilization (lowering in energy) of the d orbitals  without   a  z  component, while the orbitals with a   z  component are destabilized (higher in energy).

6. Distortions in Octahedral Geometry If the ground electronic configuration of a non-linear complex is orbitally degenerate, the complex will distort so as to remove the degeneracy and achieve a lower energy. This is called the Jahn-Teller Effect d 8 d 9 e g e g Ni 2+ : Only one way of Cu 2+ : Two ways of filling the e g orbitals; t 2g t 2g filling the orbitals; not degenerate and no Jahn- Teller Distortion T here i s degeneracy an d Jahn- T e ller Distortion is observed

7. J o hn -Teller Distortion in Cu(II) Complexes d x 2 -y 2 e g energy d z 2 d xy t 2g Cu(II) in regular octa- hedral environment d x z d yz Cu(II) after J ohn teller distortion 6 [CuF ] 4-

8. Distortions in Strong Field Ligand     Figure shows the various electronic configurations for octahedral complexes with large ΔΔ, including the low-spin configurations of d 4 , d 5 , d 6 , and d 7 . The electron configurations highlighted in red (d 3 , low spin d 6 , d 8 , and d 10 )  do not  exhibit Jahn-Teller distortions. On the other hand d 1 , d 2 , low spin d 4 , low spin d 5 , low spin d 7 , and d 9 , would be expected to exhibit John-Teller distortion.

9. Distortions in Weak Field Ligand     Figure shows the various electronic configurations for octahedral complexes with small ΔΔ, including the high-spin configurations of d 4 , d 5 , d 6 , and d 7 . The electron configurations highlighted in red (d 3 , high spin d 5 , d 8 , and d 10 )  do not  exhibit Jahn-Teller distortions

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