Firstly, you should consult a Financial Advisor when deciding to set up a pension scheme.   

Currently, if the Company pays for the contributions, you and your wife will effectively share the tax relief.  Whereas, if you make the contributions from your own income after taxes, you receive all of the tax relief.  So, if one of you is a Higher Rate taxpayer (income over £45,000) then it may be worth trying to set the tax relief against that person  

However, since April 2016, the new dividend tax has made company pension contributions much more advantageous than personal pension payments paid from dividends.