Attention,
Since you are married already, changing your wife back to accompanying might trigger following action:
1. if you do it before AOR, then you have to provide proof that you have enough points with her on the day you have received your ITA (meaning that her IELTS general and ECA must be valid on that day). If you do not have it, then your application can get cancelled (as you could not put down enough proof to cut over CRS score).
2. if you wait after AOR to add her and hope that it will not change the score, then by adding here you will be again caught to the point 1. recheck. Normally your CRS is fixed with AOR, but in this case adding her back later, might be seen as trying to walk around the system and if you cannot proof enough points, you might end up in misinterpretation.
I would not even suggest to keep that ITA if you want to include your spouse and if currently with her included you have less than min. ITA points required.
And not having a valid marriage certificate issued yet does not change the fact, that you were married at the moment of ITA.
See more info here:
http://www.cic.gc.ca/english/resources/tools/perm/express/refuse.asp