As long as it's not critical that you don't have a perfectly watertight seam, you can get away with this. I've used acrylic in glass tanks for both sumps and overflows without a problem. I just find it easier to work with. Basically, the silicone adheres very well to the glass and is then able to anchor the acrylic in place (and does stick to it to some degree). If done correctly, it's pretty watertight and quite secure. Just try go get silicone on both sides of the acrylic if possible.
As for type, any aquarium safe silicone will do. GE Silicone 1 is supposed to be reef safe, but I hear rumor every once in awhile that they put mildew inhibitors in some of those as well, so I usually just stick with the silicone for aquariums you can find at Lowes. It's a little more expensive, but with the realitively small amounts I use, the peace of mind is well worth the additional cost.