I used the suggestion of a full closing of the game, logging in, and then entering practice tool for testing. I did several rounds of testing since this happens to me as well. (Windows 7). I was reliably replicating the issue.
In my particular case I've observed the following behavior. (This all being after the release of the new login/client system.)
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The first instance of me using Mouse 4 or Mouse 5 in game resulted in an alt-tab event to desktop. Mouse 1-3 all work fine. I even went so far as to run down the keyboard and hit every key but no single key press caused an alt-tab event.
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After the first use, it does not happen again unless I close out of League completely. Even with the "Close client during game" option enabled it seemed not to be occurring again so long as my current login session was still alive.
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I tested the suggested solutions and none of them appeared to change this behavior.
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It even happens as early as the loading screen. This can be leveraged to get that first alt-tab out of the way before the match begins.
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In my practice tool tests I did not observe any activity at the desktop once the alt-tab completed. (The old Windows Key alt-tab in some games would pop the start menu, for example)
I have not had this kind of issue with any other games other than the ol' Windows key nonsense (so I popped that key off my keyboard). I'd guess it's something to do with the "League of Legends*32.exe" process or perhaps a related config file that works with it. Mouse 4 and 5 (in my case) can operate as forward and back buttons while browsing folders (Explorer.exe) and in web browsers like Chrome. (Not sure if related to the interaction we're seeing here.)
Is anyone seeing it happen more than once per session or is it only the first click like in my case?
Hope this helps Rito!