before you venture into pouring any metals in any form, get used to pouring hot materials in general. Ive seen people pour molten metal into molds that had some residual moisture in them, not nice.
Its very simple to cast up a coin in silicone. If its not a vintage coin or you dont care about the surface, use a dab of hot glue to hold the coin flat on a flat surface. Also get a couple hardware nuts (from nuts and bolts fame) and hot glue those around the coin. These will be your mold keys and lock the mold halves in place. Use a wax paper cup (cold drink cup) as the mold box and hot glue that to the flat surface with the already affixed coin in the center. Pour your silicone and side one is done. If your lucky the coin will snap off the surface and stay in the silicone to do side two, if not just realign it in place. Remove the hot glue, Vaseline the already cured silicone, use another wax cup pressed onto the mold half and hot glue it in place, pour your second half, done.
The trick and learning curve is in the pour. For metal I simply use a round sharpened hollow metal tube to cut a hole in one side of the mold. Usually on a raised surface or somewhere its easy to grind flat and polish away when removing the excess metal sprue.
What you should start with to learn pouring hot materials is simple, crayola crayons. You can melt them on the stove in a cut open soup can in seconds. It will pour like metal and is inexpensive to practice with. Use only crayola crayons though as cheapies and most other brands will not melt the same nor will they stay together most of the time when pulled from the mold.
For a gag I had to make silver coins that would melt quickly and pour into a bullet mold all in one shot. Crayons are the savior. Here are a few double sided crayon coins that were tests. The color is off but its the colors I had on hand for the tests. Its strait out silver crayons with a little silver metal powder in for nothing more than a metallic look when melted. I let the mold cure in the fridge since these had to be done in minutes.
Real coin on top left, crayon coins on the right, lower left is a coin I poured in plastic.