When I highlight text I want to replace with a WP symbol, the insert symbol toolbar button becomes unavailable. I have to delete the text, then select "insert symbol" to insert the symbol. I can't think of any reason why the button should disappear when I highlight text. This may be a small matter, a mild annoyance, but it makes no sense. Hopefully, it will be an easy bug to repair.
Insert>Symbol is still available and so is Ctrl-W.
No toolbar is anyway involved. You are looking at the Property Bar, which is designed to vary with context.
You can add that icon to the Selected Text Property Bar if you so wish.