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In LR 4/5, in the previously called "Split Tones" panel, pressing alt when moving the Hue slider would show the hue with 100% saturation. That was very helpful to quickly get the right color.
Today, in the revamped Color Grading tool, the alt key doesn't affect the Hue anymore.
Workaround: set saturation manually, set hue, revert saturation.
However, if I'm happy with my saturation, doing so means I have to remember the value I was at.
It is also extra steps that are not necessary.
M1 MBA / macOS 12.2.1 / LR 11.2
Note that setting saturation to 100 is easier than trying to keep the dot on the edge of the wheel.
If deviating from the edge, the saturation changes which can give a wrong feeling in what color is being set.
I suspect this is due to the color model being used where Saturation is separate from Hue by design.