Update.... and it might answer some of the questions from above

Well waking up at 5.30 I found 1 PE seat had become available on the second flight I booked so I called up and added my amex upgrade voucher and bagged that seat. So as of 6am the Wife was in UC and I was in PE on a flight leaving a few days later than the original one we wanted.
We were fairly happy with this and then spotted when going to work 2 PE had become availble the day before this flight. After a chat with the wife we decided that we would regret one of us not being in UC so left it.
By the time i got to my desk a PE seat for the original flight I wanted us to be on had become availble so straight onto the amazing flying club (the last 3 calls have been excellent) who did all the hard work.
When I mentioned what I needed to do - change the upgraded PE flight that was in my name and move it to the first flight in my wifes name she said it would be a £25 change fee and £50 name change fee. I asked about cancelling and booking again.
She said thats not a problem, refunded all my miles, fees and reward upgrade and did the booking again. It cost £30 to do this, there was no problem with getting my miles back and there was no problem re-using my reward upgrade.
All good so far, just got to keep my eye out for a UC to upgrade the wife to or let her have my seat if I cant get her UC on the way home. Thanks to everyone here for answering questions and sorry if I have rambled on
