Originally Posted by
GrumpyDiver
I don't use Lightroom a lot, but the develop functionality is quite similar to Adobe Camera Raw.
The answer is that the desaturaration slider takes all colour out using a brute force method where the colour content of all channels is cranked down equally, whereas the B&W setting bias of different colours giving a more "natural" look. You will see this if you look at how the HSL tab works rather than the Basic tab.
Play with the HSL sliders and see how it affects your final image.