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Answer for Federal

Short answer: Yes, she’d qualify for compassionate care leave.
In many jurisdictions, employees must have minimum service to be eligible for family and other leaves. Employees who are probationary wouldn’t, by definition, qualify. Unfortunately/Fortunately–depending on your point of view–compassionate care leave for federally regulated employees applies to “all employees.” There are no minimum service eligibility requirements. At least I couldn’t find any and I checked the Canada Labour Code statute, regulations and government guidance. I could have missed something, but I don’t think I did.