A 50% solution of ethylene glycol and water has a boiling temperature of 107 C at atmospheric pressure (versus 100 C for straight water).
A radiator cap with a release pressure of 1 bar (most of them are +/- that range) on top of atmospheric pressure of approximately 1 bar thus gives an absolute pressure of 2 bar, at which point the boiling temperature of straight water is about 120 C. Glycol will be higher but I don't have information on the simultaneous effects of both pressure and glycol concentration.
In other words, in terms of resisting boil-over, having a functioning radiator cap is a bigger factor than the use of glycol or not.
I know of no vehicle manufacturer that sets their thermostat opening temperature or their cooling-fan switch-on temperature much beyond 100 C. No one cuts it that close in terms of approaching the boiling temperature.
At least in the motorcycle world, for production bikes, which have very constrained radiator sizes and airflow, idling or puttering along in slow traffic in hot weather is usually more of a limiting case than high-power-output operation. Having said that, at Superbike levels of performance (and usage), they often have radiators bigger than standard because they have to cope with full power output in Qatar, or southern Spain, under racing conditions. Some manufacturers have tried using very high-pressure cooling systems in MotoGP in the interest of being able to reduce the amount of airflow through the radiator for aerodynamic reasons.
Cars and trucks these days have huge radiators. There's lots of headroom to accommodate sitting in traffic in hot weather with the air conditioning on full blast ... or for having off-spec coolant mixtures (i.e. water). It's rare to see someone pulled over at the side of the road with the hood up and steam coming out - nothing like how it was 40 or 50 years ago.