I think I got it
Canging the 0 to 2 here "TCA_SINGLE_CMP2EN_bm" and "CMP2BUF", selecting PIN2 as output worked. The other three output pins only work in dual PWM mode as far as I can tell so using WO2 in dual mode will mean WO5 is the other active pin. The frequency is 5x lower than what I calculated it should be, but I guess that's just some other config I need to look at elsewhere in my code.
RE: Modern PIC: I've not used a PIC in about 10 years, but I will have a look at that next time as that PPS does look handy.