Without having actually looked into it (though I mained a Rogue back in the early 2000's and again here on this server), I'd estimate that the chance per backstab/throw is the same; the difference being that you can throw far more often than you can backstab.
The only caveat is you have to be behind the mob for throw to assassinate, so you can't just kite around throwing shurikens at things hoping for an assassination.
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