Welcome to Just Answer Chrysler my name is Mark.
No the ambient temp sensor is not going to stop the a/c from working so you will need to concentrate on the actual cause.
Does the compressor cycle on and off?
Maybe this is just low on freon........have you had it checked?
Since I can't be there to see this wire connector, it could be an extra in the harness that is not used on your particular vehicle.
Fog lamps is one option that comes to mind........the wiring may be there but no lamps.
As for the a/c, do you know the pressure readings in the system......both high and low system pressures. If you can find those out we can go from there.