Which of the following has longest C-O bond length? (Free C-O bond length in CO is 1.128 A.)
As negative charge on metal carbonyl complex increases, back π -bonding increases and hence bond length of C-O bond increases while bond length of metal-carbon bond decreases.
Hence, [Fe(CO)4]2− has longest C-O bond length among the given complexes.
The correct order of bond length of the given complexes is
[Mn(CO)6]+<[Ni(CO)4]<[Co(CO)4]−<[Fe(CO)4]2−