Which of the following complexes exhibits the highest paramagnetic behaviour? Where gly = glycine, en =…

Which of the following complexes exhibits the highest paramagnetic behaviour? Where gly = glycine, en = ethylenediamine and bpy = bipyridyl moities). (At. number $\mathrm{Ti}$ $=22, \mathrm{~V}=23, \mathrm{Fe}=26, \mathrm{Co}=27$ )
  1. $\left[\mathrm{Ti}\left(\mathrm{NH}_3\right)_6\right]^{3+}$
  2. $\left[\mathrm{V} \text { (gly) } 2(\mathrm{OH})_2\left(\mathrm{NH}_3\right)_2\right]^{+}$
  3. $\left[\mathrm{Fe}(\mathrm{en})(\mathrm{bpy})\left(\mathrm{NH}_3\right)_2\right]^{2+}$
  4. $\left[\mathrm{Co}(\mathrm{OX})_2(\mathrm{OH})_2\right]^{-}$

Solution

The electronic configuration of \(V(23)=[A r] 4 s^2, 3 d^3\) Let in \(\left[V(\mathrm{gly})_2(\mathrm{OH})_2\left(\mathrm{NH}_3\right)_2\right]^{+}\)oxidation state of \(V\) is \(x\). \(\begin{aligned} & x+(-1) \times 2+(-1) 2+(0 \times 2)=+1 \\ & x=+5 \\ & V^{5+}=[A r] 4 s^0, 3 d^0 \text { (no unpaired electrons) } \end{aligned}\) The electronic configuration of \(F e(26)=[A r] 4 s^2, 3 d^6\) Let the oxidation state of \(F e\) in \(\left[\mathrm{Fe}(e n)(p p y)\left(\mathrm{NH}_3\right)_2\right]^{2+}\) is \(x\) \(\begin{aligned} & {[x+(0)+(0)+(0) \times 2]=+2} \\ & x=+2 \\ & F e^{2+}=[\mathrm{Ar}] 3 d^6(\because 4 \text { unpaired electron }) \end{aligned}\) but, bpy, en and \(\mathrm{NH}_3\) all are strong field ligands, so pairing occurs and thus, \(F e^{2+}\) contains no unpaired electron. The electronic configuration of \(C o(27)=[A r] 4 s^2, 3 d^7\) Oxidation state of Co in \(\left[\mathrm{Co}(\mathrm{Ox})_2(\mathrm{OH})_2\right]^{-}\) \(\begin{aligned} & x+(-2) \times 2+(-1) \times 2=-1 \\ & x=+5 \end{aligned}\) \(C o^{5+}=[A r], 3 d^4\) [4 unpaired electrons] ox and \(O H\) are weak field ligands. The electronic configuration of \(T i(22)=[A r] 4 s^2, 3 d^2\) Oxidation state of \(T i\) in \(\left(T i\left(\mathrm{NH}_3\right)_6\right]^{3+}\) is 3. \(T i^{3+}=[A r] 3 d^1 \text { (one unpaired electron) }\) Hence, complex \(\left[\mathrm{Co}(\mathrm{Ox})_2(\mathrm{OH})_2\right]^{-}\) has maximum number of unpaired electrons, thus show maximum paramagnetism.

Asked in: NEET 2008 (Mains)

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