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NEET CHEMISTRYHard

Which of the following complexes exhibits the highest paramagnetic behaviour? where gly = glycine, en = ethylenediamine and bpy = bipyridyl moieties (At no: Ti=22\text{Ti} = 22, V=23\text{V} = 23, Fe=26\text{Fe} = 26, Co=27\text{Co} = 27)

A

[V(gly)2(OH)2(NH3)2]+[\text{V}(\text{gly})_2(\text{OH})_2(\text{NH}_3)_2]^+

B

[Fe(en)(bpy)(NH3)2]2+[\text{Fe}(\text{en})(\text{bpy})(\text{NH}_3)_2]^{2+}

C

[Co(ox)2(OH)2][\text{Co}(\text{ox})_2(\text{OH})_2]^-

D

[Ti(NH3)6]3+[\text{Ti}(\text{NH}_3)_6]^{3+}

Step-by-Step Solution

Paramagnetic behaviour depends on the number of unpaired electrons (nn). (A) In [V(gly)2(OH)2(NH3)2]+[\text{V}(\text{gly})_2(\text{OH})_2(\text{NH}_3)_2]^+, assuming gly is the glycinato ligand (charge 1-1) and OH\text{OH}^- is hydroxo (charge 1-1), V is in the +5+5 oxidation state (x22+0=+1    x=+5x - 2 - 2 + 0 = +1 \implies x = +5). Thus, it has a 3d03d^0 configuration (n=0n=0). (B) In [Fe(en)(bpy)(NH3)2]2+[\text{Fe}(\text{en})(\text{bpy})(\text{NH}_3)_2]^{2+}, Fe is in the +2+2 oxidation state with a 3d63d^6 configuration. Since en, bpy, and NH3\text{NH}_3 are strong field ligands, the complex is low-spin (t2g6t_{2g}^6) with n=0n=0 (diamagnetic). (C) In [Co(ox)2(OH)2][\text{Co}(\text{ox})_2(\text{OH})_2]^- (intended as [Co(ox)2(OH)2]3[\text{Co}(\text{ox})_2(\text{OH})_2]^{3-} to account for the stable +3+3 state of Co), Co has a 3d63d^6 configuration. Because OH\text{OH}^- and ox2\text{ox}^{2-} act as weak field O-donor ligands in this context, it forms a high-spin complex with n=4n=4 unpaired electrons. (D) In [Ti(NH3)6]3+[\text{Ti}(\text{NH}_3)_6]^{3+}, Ti is in the +3+3 oxidation state with a 3d13d^1 configuration (n=1n=1). Since the cobalt complex has the maximum number of unpaired electrons (n=4n=4), it exhibits the highest paramagnetic behaviour.

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