In metal carbonyls, the bond between the metal and carbon possesses both σ and π character. The M-C π bond is formed by the donation of a pair of electrons from a filled d orbital of the metal into the vacant antibonding π∗ orbital of carbon monoxide (back-bonding).
- Effect of Back-Bonding: Filling the antibonding π∗ orbital of CO weakens the C-O bond, decreasing its bond order and increasing its bond length.
- 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∗ orbital of CO.
- Comparison:
[Fe(CO)4]2−: Iron has a formal charge of −2. (Highest electron density). [Co(CO)4]−: Cobalt has a formal charge of −1.
Ni(CO)4: Nickel has a formal charge of 0. [Mn(CO)6]+: Manganese has a formal charge of +1. (Lowest electron density).
- Conclusion: Since [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 .