What makes dimethyl compounds so extreme?
This is because of two trivial facts, one from chemistry and another from math: (1) methyl is the smallest organic radical, and (2) it is not uncommon for a function to reach an extremum at the border of its domain.

Arguably, this is not even true in any significant way. Not sure about DMSO, but I firmly believe that organic compounds of mercury are all about as deadly as dimethylmercury. Well, those with bigger organic radicals might be slightly less dangerous because they are not quite as good at penetrating the cell barriers, or lower solubility, or because they contain less mercury per gram. The maximum is probably reached at methyl; but the maximum is not sharp.

All that applies to pyrophoric metalorganics as well.

So it goes.