I'll check, although I doubt it.

MS PAINT is very limited.
*** ETA *** 'Help' on MS Paint says 'This Content is no longer available' - isn't that great? There is a 'Resize' and a 'Skew' function, but of course now there is no way of knowing if it will center an existing image if you change the size of the canvas ...
I did go back and position it as best I could (3 pixels out of alignment to the lower right corner) and re-draw a new outer border - which I always do in a different color to start. I 'erased' the black border that extended past it on two sides, then painstakingly went in to touch up the colors touching the new border. Then I changed the new border back to black. It is now aligned & centered ... and saved!