Leaves from oak, beech and maple are said to be safe; I use oak as I have an oak tree. Make sure they are completely dry, meaning that they fall from the tree naturally when dead (as in the autumn, this is the first "dry" as the leaf will contain no liquid) and you can collect them and lay them out to dry (the second "dry"). Other leaves may be safe too, I will leave that for other members to say, but these three are fine provided they have no pesticides, fertilizers, etc.
I do not boil the leaves I collect, as I know they have no chemicals, and boiling will naturally remove much of the benefit you are after. You can give them a quick rinse before laying them out on paper towelling to dry (not newsprint as the leaves can absorb the ink).
Leaves like any plant matter will leech tannins. This can affect the pH (by lowering it, making it more acidic) depending upon the amount of leaves, water volume, and initial GH and pH of the water in the aquarium. With soft water fish this is not going to cause any problems. The tannins leaves release do benefit by acting as an inhibitor of some bacteria; some fish suppliers put leaves in with fish for transport. The leaves also cause infusoria, microscopic live food on the surface as the leaf breaks down, and this is excellent food for fry. My 10 gallon tank is home to growing Farlowella vitatta fry and my pygmy corys which spawn regularly, and several fry survive largely by eating this infusoria. The Farlowella are always browsing over the leaves and this is their main food source.
Byron.