open an administrative power shell session and pop your new key in using the dism tool

dism /online /set-edition:ServerDatacenter /productkey:<Datacenter key, e.g. AAAAA-BBBBB-CCCCC-DDDDD-EEEEE> /AcceptEula


http://community.spiceworks.com/how_to/show/30293-howto-switch-from-windows-server-2012-standard-server-to-windows-server-2012-datacenter-server-without-having-to-reinstall


 

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