Note that you should most likely use "A unit starts the effect of an ability" as your Event. This is because Begins casting an ability will fire the trigger regardless of whether the ability actually goes off. For instance, if you issue a Stop command immediately after you begin casting the ability, the trigger will run, but the ability won't go on cooldown.
Anyway, in order to create an effect like this you should learn how to use Dummy units. A dummy unit is a unit based on the Undead's Locust. This unit is useful because it has the Locust ability, which makes the unit unselectable and therefore "hidden" if setup properly. I attached a map with a Dummy unit that you can copy and then paste into your own map.
And here's how you can make Ensnare "stun" using a Dummy unit.
After importing the Dummy unit, create a new ability ability based on Storm Bolt and modify it so:
1) It has no missile art and it's missile speed is the same as Ensnares.
2) It has 0 damage, 0 mana cost, 99999 cast range, and the same Targets Allowed as Ensnare.
This way the Dummy will be able to cast it.
Then create this trigger:
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Ensnare Stun
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Events
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Unit - A unit Starts the effect of an ability
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Conditions
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(Ability being cast) Equal to Ensnare
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Actions
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Unit - Create 1 DUMMY for (Triggering player) at (Position of (Triggering unit)) facing Default building facing degrees
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Unit - Add STUN ABILITY to (Last created unit)
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Unit - Order (Last created unit) to Human Mountain King - Storm Bolt (Target unit of ability being cast)
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Unit - Add a 1.00 second Generic expiration timer to (Last created unit)
How it works:
So when our unit casts Ensnare we create an invisible/unselectable Dummy unit at the position of the casting unit. This Dummy is given the custom Storm Bolt ability we made and ordered to cast it targeting the Ensnare target. This results in the target getting hit by 2 abilities, your Ensnare ability, and the Storm Bolt ability, causing the target to be both ensnared and stunned.
Note that this trigger leaks a Point. This isn't something I would worry about just yet, but once you're more experienced with the editor you should look up Memory Leaks and see how you can design your triggers to avoid them.