Ok, rotating by Pi radians sort of works. Although not quite, I had to offset slightly, something like:
Sprite.Transform = Matrix.RotationYawPitchRoll(Math.PI - 0.0001F, 0.0F, 0.0F)
Which seems to work, but now the sprites do not appear in the order you call Draw in, the slight modification of PI to force it to draw seems to be causing all flipped sprites to "go to the back".
Any ideas?