I don't know how it is the U.K., but the primary government minted silver coin here in the U.S., the Silver Eagle, is legal tender and, in theory, can be spent anywhere. Of course it's kind of dumb to spend a 1 oz. silver coin as if it were a dollar but you could. I'm hanging on to my silver eagles though so I'm not going to try. :)
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These coins were minted as legal tender but I'm really struggling to find anyone that 1) even knows what the coins is let alone 2) take it as payment
I guess technically they don't have to take it as payment unless it is for a debt you already have. Personally, I'd jump at the chance to take it as payment at face value :).