Just what exactly is so exciting about playing with Rioters? You CAN'T cuss at people or call them a noob and you CAN'T go Away From Keyboard if you don't feel like playing anymore. If you do they might punish you ON THE SPOT. Riot employees are like you and me, but works for Riot and probably only makes on average 20-25 bucks and hour....Its not like you're playing this game with your favourite celebrity or Kim Jong Un, nothing exciting, or "WOW" about it.
The only time I would ask to play with them is if I'm banned or chat restricted, then be super nice in game with them. After that I convince them that I am a nice guy and get punishments removed. OR if I'm planning to work for Riot so I play a game with them just so that I can keep in touch and ask questions easier. LOL :D