You can only assign a person or group to an account that has been placed into collections. If the account is NOT in collections, the Edit Assigned To option does not appear in the shortcut menu.
To assign a person/group to an account that is in collections or change the person/group currently assigned to an account in collections:
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Right-click anywhere in the Collections Information section of this window and select Edit Assigned To. This displays the Assign Account window.

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Select the person or group to which you want to assign this account from the drop-down list and click Save. This updates the Assigned To field in the Collection Detail and Collections History tabs to reflect your change.