I can assign any skill to any any skill slot, except the primary skill slot (left mouse button). A few skills cannot be slotted there, for no apparent reason. For instance, Fan of Knives.
Does anyone know why this is so?
Because left click also works as navigation button (go here or there). That can conflict with some skills. So those skills have been greyed out.
Also be sure you have Elective Mode enabled in the options / settings menu.
I understand what you’re saying, but this conflict occurs with any skill, even the primary skills that are “designed” to go there. Using “forced stand” resolves this for all skills that can be slotted there. My issue is with skills that are grayed out for the primary skill slot (elective mode enabled).
Why is this the case only for Fan of Knives and all “Defensive” skills, for Demon Hunter? For Wizard no skills are grayed out, so it’s inconsistent for the various classes.
I can see no reason for disabling some skills for the left mouse button.
You are discussing two different issues.
This isn’t a bug or a conflict. The left mouse button does double duty. If you click on a monster, it will activate whatever skill is assigned to it. If you click on open ground, it causes your character to move there. Using the “force stand” button forces your character to use the skill assigned to the left mouse button, even if no monster is targeted.
Some skills are not able to be assigned to the left mouse button. For whatever reason, Blizzard made this decision. Nothing you can do about it.
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You’re input is appreciated. You basically confirmed what I already knew, and I agree with your assessment that “For whatever reason, Blizzard made this decision. Nothing you can do about it.”
I guess the reasoning behind it will remain a mystery. 
Doesn’t this change left mouse click to not move forward (and cast skill) as it used to before changing to “force move” ?
They are two separate options. Force Stand stops the left click key from moving and only activates whatever skill is assigned at the indicated location. Force Move stops the left click key from activating it’s skill and will move you to that location even if a target was available there. They each override the dual nature of the left click key to only do one or the other depending on which “force” option is activated.
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