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i have read that NH3 act as a SFL with M+3 oxidation state and act as a WFL with M+2 oxidation state.Also it is stated that when NH3 forms a complex with M+2 oxidation state its stability constant is 10^11 and when h20 forms a complex with M+2 oxidation state its stability constant is 10^15, though in spectrochemical series NH3 is far ahead of H20 (Source-Triump chemistry ,target publications) So,if that is to believed then [Ni(H2O)6]^2+ should be more stable then [Ni(NH3)6]^2+ as Ni is in +2 oxidation state.Now coming to the crux question, we need to arrange the complexes in correct order for the Wavelength of absorption in the visible region (PYQ- AIIMS 2005) the options are [Ni(NO2)6]^4-

Siddharth bisht , 4 Years ago
Grade 12
anser 1 Answers
Askiitians Tutor Team

Last Activity: 13 Days ago

To tackle your question about the stability and absorption wavelengths of different nickel complexes, we need to break down the concepts of ligand field theory and the spectrochemical series. Your observations about ammonia (NH3) and water (H2O) as ligands are insightful, and they lead us to an interesting discussion about the nature of these complexes.

Understanding Ligand Field Theory

In coordination chemistry, ligands can be classified based on their ability to split the d-orbitals of the metal ion. The strength of this splitting is influenced by the nature of the ligands involved. In the spectrochemical series, ligands are arranged according to the strength of the field they produce, which affects the energy difference between the split d-orbitals.

Comparing NH3 and H2O

Ammonia is indeed a stronger field ligand than water, which means it causes a greater splitting of the d-orbitals in transition metal complexes. However, the stability constants you mentioned indicate that the overall stability of a complex is not solely determined by the ligand's field strength. The stability constant for [Ni(H2O)6]^2+ being higher than that for [Ni(NH3)6]^2+ suggests that the interaction between nickel and water is more favorable in this case, despite NH3 being a stronger field ligand.

Absorption Wavelengths and Color

The absorption of light in the visible region by these complexes is directly related to the energy difference between the split d-orbitals, which in turn is influenced by the ligand field strength. Stronger field ligands like NH3 will typically lead to larger splitting and thus absorb light at shorter wavelengths (higher energy), while weaker field ligands like H2O will result in smaller splitting and absorb at longer wavelengths (lower energy).

Arranging the Complexes

Now, let's focus on the specific complexes you mentioned. The complexes in question are:

  • [Ni(NO2)6]^{4-}
  • [Ni(NH3)6]^{2+}
  • [Ni(H2O)6]^{2+}

To arrange these complexes in order of their absorption wavelengths, we need to consider the ligand field strength:

  • [Ni(NO2)6]^{4-} - Nitrite is a strong field ligand, likely leading to significant d-orbital splitting and thus absorbing at shorter wavelengths.
  • [Ni(NH3)6]^{2+} - Ammonia is a moderate field ligand, resulting in a moderate level of d-orbital splitting and absorption at intermediate wavelengths.
  • [Ni(H2O)6]^{2+} - Water is a weaker field ligand, leading to the least splitting and absorption at longer wavelengths.

Based on this analysis, the order of absorption wavelengths from shortest to longest would be:

[Ni(NO2)6]^{4-} < [Ni(NH3)6]^{2+} < [Ni(H2O)6]^{2+}

Final Thoughts

This arrangement reflects the relationship between ligand strength, d-orbital splitting, and the corresponding absorption wavelengths. Understanding these concepts is crucial in predicting the behavior of transition metal complexes in various chemical environments.

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