Catch-up contributions do not count towards the annual additions limit.
Wife defers $26,000 (assuming we're talking 2021 limits here). That exceeds the 402(g) limit so $6,500 is reclassified as catch-up. The remaining $19,500 does count against the annual additions limit.
Her annual additions limit is the lesser of $58,000 or 100% of comp. In this case that's $28,400.
The amount she has left under the annual additions limit is $28,400 - $19,500 = $8,900. That is the maximum employer contribution that could be allocated to her for 2021.
That does exceed 25% of comp, but remember that the 25% deduction limit is applied on an employer-wide basis. $103,090 + 28,400 = $131,490 x 25% = $32,872.50 is the deduction limit for 2021. You could allocate $8,900 to the wife and the remaining $23,972.50 to the husband, if you wanted to.
This is assuming no other employees besides the husband & wife.