Medicare As a Secondary

Have only come across this scenario a few times before. Not really sure how it works.

If someone has insurance through an employer, and their insurance acts as the primary. The company says she dont have to pick up Pt B, but she wants to anyway, so Medicare acts as a secondary. Will Medicare pick up deductibles and copays? Or would she still have to pay Medicare deductibles first, before Medicare acts as a supplement?
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