I read the MDN documentation about how to get a reference to the bookmarks tree und to navigate within. But how do I know which folder represents the bookmarks toolbar? This toolbar is named differently depending on the locale. I am not sure whether a user is still allowed to select an arbitrary folder for this, but this was possible some years ago.
I found this post: Programmatically bookmark pages in bookmark toolbar using firefox extension
but this is not about the new webextension API that everybody has to use now.
As per comments, there are special IDs you can search for.
They were apparently introduced in https://bugzilla.mozilla.org/show_bug.cgi?id=1071505 4 years ago, to be generally used by other Firefox subsystems as hardcoded values. While that can change, it's unlikely and would have be for a good reason because of all pre-existing dependencies elsewhere.
That said, their use in WebExtensions is not documented.