I just gave the roof stuff the sniff test, and I can smell a slight tar scent with my nose right up to the surface, otherwise no odor. You'd have to pretty scent sensitive for the stuff to both you.
I've used it inside speaker cabinets and CD player lids so not much concern about temperature extremes there. The stuff will likely soften at high temperatures so you wouldn't want to use it on or near heat sinks, transformers, or tubes. But you wouldn't use Dynamat for that either.