Boron Halides

Preparation:

BX3 are all planar monomeric species due to the extra B(pπ)-X(pπ) bonding (compare AlCl3, which dimerizes to give Al2Cl6, as the inter-molecular Lewis acid–Lewis base bonds are stronger than the intra-molecular bonds in BX3).Structure:

Reactions:

All BX3 are Lewis acids, with acid strength BF3<BCl3<BBr3<BI3.This reflects the loss of pπ-bonding when the BX3 distorts from planar to pyramidal on reaction with the Lewis base; the B(pπ)-F(pπ) bond is the strongest due to the small size of the F– ion, and therefore the least reactive.

Competition exists between different halides, and rapid equilibrium is set up.
Hydrolyzed to give Boric Acid [B(OH)3]

Formation of lower halides, (BX)n. These all have B-B bonds (though boron catenates less than carbon), and the dimers are all planar with D2h symmetry, except B2Cl4(g), which is D2d. Larger, cage-like structures have [3c,2e] bonds, eg. B4Cl4, which is tetrahedral, with [3c,2e] bonds making up the faces.