Modern engines normally use close-coupled catalysts. The under-floor catalyst is, for the most part, old-skool.
The modern engines emit an order of magnitude less HC/CO/NOx than what they did prior, but for sure, not all of this is from simply relocating the catalyst. I don't know of an engine family that came with both arrangements in which the repositioning of the catalyst didn't also come along with a whole bunch of other changes that make direct comparisons futile.
Powertrain engineers are applying every trick in the book to reduce emissions, particularly cold-start emissions, and bringing the catalyst close to the engine is one of them.
Mazda's Skyactiv system is a notable modern-day exception in which they had to move the catalyst out in order to accommodate a long-tube header design. But that engine uses a lot of other emission-control trickery.
Perhaps it will help to know why you are asking the question.