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Question

Suggest reasons why the B–F bond lengths in BF3 (130 pm) and BF4 (143 pm) differ.

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Solution

The B–F bond length in BF3 is shorter than the B–F bond length in BF4 . BF3 is an electron- deficient species. With a vacant p-orbital on boron, the fluorine and boron atoms undergo pπ–pπ back-bonding to remove this deficiency. This imparts a double bond character to the B–F bond.

This double-bond character causes the bond length to shorten in BF3 (130 pm). However, when BF3 coordinates with the fluoride ion, a change in hybridisation from sp2 (in BF3) to sp3 (in BF4) occurs. Boron now forms 4σ bonds and the double-bond character is lost. This accounts for a B–F bond length of 143 pm in BF4 ion.


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