Your £5,000 won't quite get you a last-generation S-Class, which even today still looks thoroughly modern (you'll need up to £10k for a good one of those), but a W140 from around the mid to late '90s could be yours. It's showing its age a little now, but really, that just means is it's getting more classic and much cooler. Built in the era before Mercedes started cost cutting and took a bit of a nosedive in quality terms, the W140 is a 'proper' Merc: rock solid, reliable, comfortable and big.
The S 320 was the base model when it was unveiled in 1994, though its six-cylinder, 228bhp engine has more than enough power to pull the big Merc along quietly and swiftly, even though its automatic 'box has a mere four gears - some Mercs have seven these days. Owners of early models complained about oil leaks and dodgy door seals, but those problems were ironed out for later versions and other issues were sparse. As always, make sure you get one with a full service history, preferably from a Mercedes dealership, although that's not essential as long as the service book is properly stamped and the previous owners have adhered to the service intervals.