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NEET CHEMISTRYMedium

Which of the following has the longest C-O bond length? (Free C-O bond length in CO is 1.128 Å.)

A

[Co(CO)4][Co(CO)_4]^-

B

[Fe(CO)4]2[Fe(CO)_4]^{2-}

C

[Mn(CO)6]+[Mn(CO)_6]^+

D

Ni(CO)4Ni(CO)_4

Step-by-Step Solution

In metal carbonyls, the bond between the metal and carbon possesses both σ\sigma and π\pi character. The M-C π\pi bond is formed by the donation of a pair of electrons from a filled dd orbital of the metal into the vacant antibonding π\pi^* orbital of carbon monoxide (back-bonding).

  1. Effect of Back-Bonding: Filling the antibonding π\pi^* orbital of CO weakens the C-O bond, decreasing its bond order and increasing its bond length.
  2. Charge on Metal: The extent of back-bonding depends on the electron density on the central metal atom. A higher negative charge on the metal facilitates greater donation of electrons into the π\pi^* orbital of CO.
  3. Comparison: [Fe(CO)4]2[Fe(CO)_4]^{2-}: Iron has a formal charge of 2-2. (Highest electron density). [Co(CO)4][Co(CO)_4]^-: Cobalt has a formal charge of 1-1. Ni(CO)4Ni(CO)_4: Nickel has a formal charge of 00. [Mn(CO)6]+[Mn(CO)_6]^+: Manganese has a formal charge of +1+1. (Lowest electron density).
  4. Conclusion: Since [Fe(CO)4]2[Fe(CO)_4]^{2-} has the highest negative charge on the central metal, it exhibits the maximum back-bonding, resulting in the weakest C-O bond and thus the longest C-O bond length .
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