The first thing is look for
instructions and read this seems to be the existing programmer
note it says Centaur Plus is volt free, so it seems the centaur plus is same as Hive single channel and standard one is same as Hive duel channel, so I would be hunting on the actual device to see if there is a diagram. Your picture clearly shows a brown sleeve on the blue wire going to 3 so clearly a line not neutral.
You also need to look at boiler instructions, what I do is use the "find in this page" function and look for "opentherm" and "ebus" and "bus" as key words to find if the boiler should be using an old fashion digital wall thermostat (off/on) or modern modulating analogue thermostat, most boilers can use the old on/off as well, but it will not run as efficiently, Hive does have a work around using on/off only, but also needs the Hive TRV heads to work efficiently which work out expensive.
You also need to look for motorised valves, since the standard method is the programmer supplies the thermostat, and the thermostat supplies the motorised valve and the valve has a micro switch which turns on boiler so boiler can't run until valve is open, if some one has left the old wiring in place you may have a valve working like a relay, you can't assume wired correctly when you have already found a programmer wired as it would have been for a system boiler.
Personally I would not modify until the summer, I would want time to locate parts, and get things fixed and not be in a panic to get heating up and running again fast.