This hack comes from Lauren Dunne Touyet. You’ll be able to instantly confirm new user email addresses without waiting for confirmation from the user.
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“When you need to change the email address on a user record, an email is sent to the new email address asking the user to confirm the change. Only when the confirmation link in the email is clicked will the change be reflected in Salesforce. This happens regardless of how you update the email address.
If you change the email address and tick the ' Generate new password and notify user immediately' checkbox (at the bottom of the edit screen) then the email address gets updated straight away.
Only down side is the user gets a new password.This is handy for sandboxes.”