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Employees are restricted at Business Group level and not at Operating Unit level. So only employees belonging to the same business groups can be used to form an approval list.
So you cannot use employee from a different business group(A) to approve PO created by another employee from business group B.
Let me know if this clears your doubt.
Yes, It is possible; also its depends on your Workflow how it is defined.
If your workflow looks for the approver out of the business group and generates a notification to the Approver in the BG(X) then the notifiacation would go to him for approval.