Slabs on grade usually fail by punching or large cracks that separate.
Mats usually fail by insufficient bearing capacity or rotation due to differential settlement. They are typically thick enough to preclude shear or flexural failure in the concrete.
Concentrated loads are usually more evenly distributed through the thickness of a mat than a slab due to a mats higher stiffness and rigidity.
Also, depending on the size, mats could be considered mass concrete.