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Not sure if when you say "enable email on the phone from the webmail server" but if you mean Server ActiveSync, then yes, I do this myself. There is no problem with syncing just your email over Exchange Server ActiveSync and syncing all your other data through a direct connection to the PC.
One thing that will occur is that when you are syncing to a desktop PC locally, ActiveSync will still try and connect to the Exchange Server to sync the email but it is not a problem, if it can connect then it syncs, if not, then it will just tell you it is unable to connect.
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