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Q.

Which of the following statements is incorrect?
(Given that: cycloheptatriene is abbreviated as ‘cht’ and the complexes [Ni(CO)3(cht)], [Ni(CO)2(cht)] and [Cr(CO)3(cht)] follow 18 electron rule)

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a

For the complexes [Fe(CN)6]3 and [Fe(CN)6]4, the CN stretching  bands(in cm1 ) (corresponding to the highest energy) observed as [Fe(CN)6]3>[Fe(CN)6]4

b

‘cht’ ligand behaves as two electron donor, four electron donor and six electron donor respectively in [Ni(CO)3(cht)], [Ni(CO)2(cht)] and [Cr(CO)3(cht)] complexes.

c

cis and trans isomers of the complex CoCl3.4NH3 have green and violet colours respectively.

d

In CoCl3.6NH3, the primary valence of cobalt is satisfied by three Cl ions where  as in CoCl3.4NH3, two Cl ions satisfy both primary and secondary valences of cobalt.

answer is B.

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Detailed Solution

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(i) [Co(NH3)6]Cl3 and [CoCl2(NH3)4]Cl

(ii) cis form is violet coloured and trans form is green coloured complexes

(iii) [Ni(CO)3(cht)] :10+6+x=18; therefore ‘cht’2 electron donor

[Ni(CO)2(cht)]:10+4+x=18; therefore ‘cht’ 4 electron donor

[Cr(CO)3(cht)] :6+6+x=18; therefore ‘cht’ 6 electron donor

(iv) In [Fe(CN)6]3, the iron is +3, so its formal charge in the complex is '3'

In [Fe(CN)6]4, the iron is +2, so its formal charge in the complex is '4'.

Therefore, the extent of back donation is greater in the [Fe(CN)6]4 complex. 

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