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Come on guys I know you have some feedback!
This same thing just happened to me this morning. I have played this game for over 350 hours with no key binding crash issues until now. Here's my story . . .
I had just finished Dead Money, and when I returned to the Mojave and retrieved my old weapons, I could not re-bind them to my number keys without crashing. Tried maybe 5-6 times, crashed everytime. I did not have any key bind crashes while playing Dead Money. After searching the forum for help (and only finding your thread, spud), I thought I would try some experimenting with re-loading of previous saves.
I reloaded a save just before I exited the courtyard in Dead Money. I tried a few weapon changes and key bindings with no crashes. So I exited the courtyard and returned to the abandoned bunker. Here I also changed a couple of weapons and re-binded some, without a crash. I then exited the bunker back to the Mojave, returned to Novak to get my Ratslayer, etc. and now, magically, I seem to be able to rebind without crashing.
So, I think my issue has resolved, but I don't know how or why. Maybe for you, spudwinkle, try the re-load/re-bind thing. Maybe the game engine just needs to be nudged in the right direction. Who knows? My fingers and toes are crossed because I got more gaming to do.