Certain podcasts I can download on the phone but not from the desktop

This is might sound weird so I apologize if I confuse people.
Tekzilla has separate RSS feeds for different versions of their podcast. Small quicktime, large quicktime, HD quicktime. Obviously with iTunes you can sync the iPhone with podcasts or you can download the podcast themselves over wifi on the iPhone itself. I have been able to sync the small and large quicktime versions with no trouble at all.
It's the HD quicktime version that is giving me trouble.
If I signup for the HD quicktime version of the podcast in iTunes it downloads like it is supposed to but that version of the podcast can not sync up with my iPhone ever and I get the message about how it can not be played on iPhone. Now the weird thing is I can download the HD quicktime version directly on the iPhone itself using wifi and the iTunes app on the iPhone itself and it plays with no problem at all.
My question is how is it possible that I can't sync the HD quicktime version of a podcast from iTunes yet I can download that same version over wifi and it plays perfectly?
I know there really is no point in watching the HD quicktime version on the iPhone's small screen but my point is why is it possible to download it on the iPhone and not being able to get it from the desktop version of iTunes? It sounds like there is some kind of error in the desktop iTunes app.

Hi Jeff
Thank you for your reply on my request.
Im working on 2 windows 7 computers.
The one at my work downloads fine and fast, the other never ends its "waiting to install"

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