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Hi Ryan,
Thanks for the confirmation I was doing things correctly, I had followed the deployment pack including the registry keys. Re-reading the guide though I spotted that onedrive.exe was in fact loading into appdata, after failing to run it directly it occurred to me that because MS had combined the clients my GPO in Computer Configuration\Windows Components blocking Onedrive personal was kicking in.
I guess this is an unconsidered consequence of merging the two clients because previously I was blocking Onedrive personal whilst letting for business (aka Groove) remain available. Now this is sorted I can look at the ADMX to reinstate personal blocking.
Many thanks
Baz