It seems the way we're getting to this file doesn't work unless you use "open folder" instead of "open solution".
It seems CurrentWorkspace is null when using a solution:
https://github.com/microsoft/cadl/blob/067ed4523f79b0ae40b44f546a000fc869e52cc0/packages/cadl-vs/src/VSExtension.cs#L66
It might be time to use a different file for this, but we can first check if there's an easy fix. That file has other problems: it is .gitignored by default templates and otherwise contains a bunch of temporary state that is meant to be deleted, making it a terrible place to store user settings.
cc @abatishchev