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The error seems to be caused by the launcher deciding to be a ♥♥♥♥♥♥ and not looking for XCom2.exe. In the OP's case, for example, the path ends with XCom.exe... which clearly won't exists in the XCOM2 folder.
I'm absolutely befuddled how this could even happen.
The solution is simple: symlink the file! Open a command prompt with elevated privileges (for Win7, type CMD into the start menu bar, right-click cmd and RUN AS ADMIN), then go into the game folder (c:\Program Files\Steam\SteamApps\common\XCOM2\Binaries\Win64) and issue this command:
mklink XCom.exe XCom2.exe (<-- replace XCom.exe for whatever the launcher is looking. Was XComGame.exe for me vov)
That's it! Your game executable can be found with a different name as well, and the launcher will finally do its freaking job.