I really don't see it as Rocco *VOLUNTEERING* as in
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to do the job. Michael asks him if a hit on Roth can be accomplished, he answers difficult not impossible and that's pretty much taken as an order that it's Rocco's job to do.
Of course he knows he's risking his life...but it's the nature of the business they've all chosen carries out the job, attempts to get away and fails.
Rocco did what he was delegated to do. He carried out his Don's order and was successful in killing Hyman Roth. He lost his life in the process but that sometimes comes with the territory. It had nothing to do with volunteering.
And it had nothing to do with Neri.
Apple