Place I used to work, until they fired me, we did gold directly on copper for edge fingers. It had to be thick, 100 uin or more, to keep the copper from diffusing into the gold. Seemed to work fine. I think there can be problems soldering stuff like this, not to mention it's expensive.
Old HP and Tek boards were sometimes all gold, no solder mask. I don't know how thick it was, or if they used some barrier layer under the gold.
I'm going to have a pcb house make me a bunch of double-sided copperclad scraps that are gold plated on one side. Then I can make my high-speed breadboards, and they won't tarnish.
John