Hi
Regardless of the voltage level, in simple-chip mode the MCU bus frequency can be set up to 50 MHz and so the performance of the core and peripherals is not affected.
In expanded mode, however, the maximal internal bus frequency (at 3.3V) is reduced to 25 MHz, as you can see in Table A-30 in the RM.
Regarding ADC, you can measure in range of 0-5V if VDDA = VRH = 5V and run the MCU at 3.3V (VDDR = VDDX = 3.3V). See Table A-15. ATD Operating Characteristics.
Regards
Daniel