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Also bound for the same episode are Rumer Willis, who has already shot her appearance, and Scott Wolf.
The 100th show, set to air in November, centers on the pursuit of a serial killer who targets people named Mac Taylor – the name of the character played by the show's Gary Sinese.
Daughtry – who is slated to shoot his role on Monday – has been cast as Machiavelli Taylor, described in the production notes as "an attractive 30-something year old musician."
Willis and Wolf also play characters named Mac Taylor.
Others guest-starring in the episode are Julia Ormand, actor-rapper Nelly and NFL star Marshall Faulk.
JOSH & FERGIE: ROCKED BY SCANDAL
Did he cheat with a stripper?
Married less than a year, the couple denies an Atlanta woman’s claims that she and Josh had a fling
Note that this week’s cover of PEOPLE may differ regionally
