
I can see so many good reasons for something like this and can not see a single true negative reason why not, except the cost for the person doing it :)
In the end, it is like using two different studs at different seasons but it is done in one litter?
If it is to be older bitches last litter and there are still two boys you feel would suit the bitch, you can use both and get 2 different combinations to go forward with :)
If one male is older and the sperm quality is not top knotch you have not missed a season or two trying and ending up with nothing (in the end older males have got lot to give, more "data available" about their health, possible previous offspring etc). This is actually one of the main reasons for people who I know who have used the double mating. Especially with bigger breeds, the time period you have for "using a girl" does not allow for multiple goes and bitch missing over and over again if you would like to have more than one litter from her. There are many benefits of using an older dog, people are ready to give it a go and hope they get an offspring but covering the bitch with another male means the whole season is not "missed" in trying the older dog.
If you have travelled very far and wish to try to bring in more than just one lot of "genes", in the end most people travel for this very reason, to bring something "new" in to be used in the future? The cost of travelling to a stud can amount to lot of money if the distance travelled is great...
It can give you an opportunity to see what lines might go well with your girl, if you are "out crossing" and using totally different lines and not sure what the outcome will be... This is if you are not line breeding or doing something everybody else is doing so might have some idea of the possible outcome. It might help in selecting the stud for the next litter(out of the ones you have already thought about) as if all offspring of a bitch for example show certain "area needing improvement" in that mixed litter, next time you could search for a boy who is known to usually improve on that area.
If a problem surfaces with one of the studs later and you feel you should pull the offspring from being used,you have not lost a whole litter of pups but still have some usable "material". It can be a large number losing 10 pups out of going forwards if not that many registered over all.
just few positives I can think of, I'm sure there are many more...