organic chemistry - Mechanism for reaction of Tollens' reagent with aldehydes

Upon treatment with Tollens' reagent (ammoniacal silver(I) nitrate), aldehydes are oxidised to carboxylic acid, and silver(I) is reduced to silver metal.

I am trying to find a mechanism for the this reaction online, but the only thing I can find is the balanced equation. Can someone propose or help me find the mechanism?

Answer

Here are the two half reactions:

$$\begin{align} \ce{[Ag(NH3)2]+ + e- &-> Ag^0 + 2NH3} \\ \ce{RCHO + 3OH- &-> RCO2- + 2H2O + 2e-} \end{align}$$

which together yield the overall reaction

$$\ce{2[Ag(NH3)2]+ + RCHO + 3OH- -> 2Ag^0 + RCO2- + 4NH3 + 2H2O}$$

Here is a diagram of the reaction mechanism. The carbonyl group is oxidized in the process and the $\ce{Ag^+}$ is reduced. The resultant oxidized aldehyde (now a radical cation) reacts with hydroxide to form a tetrahedral intermediate. A gem-diol like intermediate is formed via a hydrogen shift, which then continues on to the final carboxylate anion.