Ok guys,
I was having that exact same problem too. I could try a skype contact or a skypeout number with either the 001 or the +1, and it would fail.
That's when I logged into my roomates laptop (running skype, with me as a contact) and signed in on my phone. I waited for a few seconds and my contact name didn't pop online for the duration; however, after about a min or two, my name popped online and from that point on, I was able to make calls on the iPhone. So the problem seems to be that you aren't technically "online" for a short duration, which is why you aren't able to make calls.
Whether this is correct or not, it seems to be the case for me. So sadly, I have to wait a few moments to make calls, but it soon allows me to. Hopefully it'll improve with time.
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