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Here's a novel solution; it does require installing two packages and editing a (very small) config file though: In summary, you install the packages xdotool and xbindkeys:

$ yum install xdotool xbindkeys

then find out what number your favoured button is by running xev from the terminal, moving your mouse pointer to the small window that pops up, and pressing that button. Check the console for a line that starts with ButtonRelease event, and take note of the button x on the third line (in my case, it's button 8).

Close xev, and create a new config file for xbindkeys:

$ gedit ~/.xbindkeysrc

And add these lines:

"xdotool key Super_L"
release + b:8

(b:8 is the button number; replace this with yours -- also, if you want to map a different button, you'll want to replace Super_L with Menu or what-have-you). Now you'll want to run xbindkeys & from the terminal and test out your configuration.

Last step: you want to start this up at the beginning of your session, so run 'Startup Applications' (you can find it by bringing up the Overlay with your newly mapped button and typing in the app name) and adding xbindkeys as a startup application. Click 'Add', enter a name (I put in 'Bind button 8 to Start button') and the command (xbindkeys) and click 'Add'.

You're done!

Full credit goes to Jason Simanek, the author of the linked-to blog post, and the sources he's quoted.