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I don't know that much about the subject... but it could be that SMTP proxy does not work over POP and needs to be tied to AS. POutlook has always had issued when sending POP e-mail since most providers won't allow e-mails apps send e-mail through their servers if they are not on their networks.
It's what happened to me with my Roadrunner account, I'd get the same Invalid Recipients message. I tried finding solutions, I read some stuff about setting Sprint's SMTP server on the RR settings... some people made it work, I gave up since I discovered mail2web push.
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