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Exercise · Q4

Q.The C=O\text{C=O} bond length in formaldehyde (1.21 A˚1.21\ \text{\AA}) is shorter than a typical C-O\text{C-O} single bond. Explain this using the bonding picture of the carbonyl group (one σ\sigma and one π\pi bond) and state the shape around the carbonyl carbon.

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A C-O\text{C-O} single bond involves only one shared electron pair (a σ\sigma bond); the carbonyl C=O\text{C=O} bond additionally has a π\pi bond formed by sideways overlap of unhybridised pp orbitals on carbon and oxygen. This second bond pulls the two nuclei measurably closer together, which is why C=O\text{C=O} (≈1.21 A˚\approx 1.21\ \text{\AA}) is shorter than C-O\text{C-O} (≈1.43 A˚\approx 1.43\ \text{\AA}) -- exactly analogous to why C=C\text{C=C} is shorter than C-C\text{C-C}. The carbonyl carbon itself is sp2sp^2 hybridised, so it and its three attached atoms all lie in one plane with bond angles close to 120∘120^\circ.

✓Final answer

The extra π\pi bond present in C=O\text{C=O} (absent in a single C-O\text{C-O} bond) shortens the bond, and the carbonyl carbon is trigonal planar (sp2sp^2, ≈120∘\approx 120^\circ bond angles).

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