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The Racah parameter B is 460 cm −1 in [Co(CN) 6] 3− and 615 cm −1...

The Racah parameter B is 460 cm −1 in [Co(CN) 6] 3− and 615 cm −1 in [Co(NH 3) 6] 3+. Consider the nature of bonding with the two ligands and explain the difference in nephelauxetic effect.

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Answer #1

The decrease in Racah parameter indicates that there is less interaction (repulsion) between two electrons in the metal complex than there is in respective gaseous metal ions. That means the size of the orbital in the complex is greater than the free metal ion. From this we can conclude that if Racah Parameter is small then the elecron cloud is not centred on some particular atom rather the electron cloud is expanded between two atoms, i.e. the bond has covalent nature. Therefore, in the first compound the ligands are more covalently bonded than the second compound.

Nephelauxetic parameter, β = B(complex) / B(free ion)

As in both the complex the metal ion is same, B(free ion) is also same. For first complex numeretor is small compared to the second one. Hence,

  β(first complex) < β(second complex)

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