Chemistry - The acidity of boric acid

Solution 1:

I think your suppositions and observations are basically correct. On the basis of general principles, it is certainly possible to imagine that such a mechanism might be at play. If one considers the structure of boric acid, it should be readily apparent that the boron atom could be quite electrophilic and hence act as a Lewis acid: it possesses a formally vacant $p$-orbital; it is bound to highly electronegative oxygen atoms, which withdraw electron density and create a partial positive $(\delta^+)$ charge on it (though this effect may be mitigated by the oxygen lone pairs, which can donate electron density into the aforementioned $p$-orbital); and finally, it has a planar geometry that makes it quite sterically accessible to approaching nucleophiles. Such a mechanism is also lent plausibility by the well-known propensity of various other boron compounds for forming Lewis adducts and being highly susceptible to hydrolysis (where applicable).

All of that having been said, I don't think it's fair to claim that such a mechanism is "obviously" correct for the reasons given above. Such arguments are strictly qualitative, and while they're very suggestive of the possibility, they are in no sense definitive. The only way to even approach something vaguely approximating certainty is to perform experiments (perhaps in concert with theoretical computations), and even there considerable difficulty exists in reaching firm conclusions. The confirmed presence of $\ce{B(OH)4-}$ under one particular set of conditions is not sufficient proof that the mechanism involving boron as a Lewis acid is always operative, nor does it rule out other pathways. (Note that I'm not necessarily disputing that mechanism, but only pointing out that extrapolating too widely from specific experimental results has certain liabilities.) As ron points out in his answer, the issue apparently isn't settled.

Edit: I would also add that there are arguments to be made against such a mechanism. There's likely some degree of $\pi$-bonding between the oxygen lone pairs and the boron, which would be disrupted by the pyramidalization of the molecule upon formation of the intermediate Lewis adduct resulting from nucleophilic attack by $\ce{H2O}$. The associated energy penalty might be relevant to the reaction kinetics under some conditions. My instinct is that this is probably not significant, but it may be a factor worth considering. Of course, this is all speculative on my part, though I think it further demonstrates that qualitative reasoning in chemistry is rarely clear-cut, and there's an awful risk of falling prey to fuzzy thinking. Hence, rigorous experimentation and calculation are vital.

Solution 2:

At least according to this Wkipedia article (look in the "Properties" section) there is some disagreement as to the basis for boric acid's acidic properties. One set of experiments seems to favor the Lewis acid interpretation shown above in black, while the other camp suggests that the data supports the view that boric acid is both a Lewis acid and a Brønsted acid (both the blue and the black mechanisms shown above are operative).