42 V was selected as it was the highest practical voltage which remains in the SELV category (Safe Extra-Low Voltage). Curiously enought one factor delaying its launch has been agreeing on a design of battery terminal which you can't connect a pair of jump leads to (imagine the damage if you tried to jump a 12V car from 42 V - say bye bye to every electronic circuit). All automotive electrical devices are protected against 24 V (but not 42V).
The high voltage circuit should also be able to reduce vehicle weight by using thinner power cabling - higher voltage means lower current for the same power, while at the same time reducing the power losses in the wiring.
(As an aside, many manufacturers are looking into a network based system for controlling things like tail lights/brake lights/turn indicators - etc. E.g. a light cluster would receive commands from the network, meaning that you don't have to have a seperate circuit for each bulb - only a network uplink and single power input).
The other benefits are reliability - auto A/C systems are notoriously unreliable because the refrigerent leaks - it leaks from the seal where the pully enters the pump - domestic A/Cs, fridges/freezers etc, don't leak because electrical compressors can be hermetically sealed - electrical in-car A/C apart from having offering no friction load to the engine when not running, won't need regular recharging because they have lost their contents.
Finally, it seems that LED technology is reaching the point where they can realistically be used as headlights. Lumileds recently provided components for a concept car lit entirely with LEDs - and they have also recently demonstrated a 120 lumen white LED (typical head light is 1000 lumens).