At this point, I'm pushing into a place where I'm just going to switch to go because its getting to be a mess.
It’s about as bad at being a programming language or data structure serialization format, though.
There are so many things that aren't expressible in TOML that any anywhat complex system will want... it's not even a contender.
So, one problem a lot of configurations are trying to solve: modularity. I.e. how to allow different actors to change the parts of the configuration they want. Everything under /etc nowadays is of a form /etc/*.d/*.* that is all configurations are directories of multiple files with some ridiculous rules (like "prefix file names with digits so that they sort and apply in the "right" order etc.) XML had a better approach with namespaces and schema, but maybe not perfect.
Polymorphism. Any non-trivial configuration system will have plenty of repeating parts. NetworkManager connection configurations? -- They are all derived from the same "template". Systemd device services -- same thing, they are all coming from the same "template". There are plenty more examples of this. But, languages like YAML or TOML don't have a concept of polymorphism in them. This is never encoded in the configuration itself. Instead, every tool that needs to be configured and needs some degree of polymorphism rolls its own version.
Constraints. It's often impossible to describe the desired configuration through specifying the exact values. Often the goal can be described as "less than" or "given the value of X, Y should be multiple of X" and so on. Such concepts, are, again, not expressible in TOML or YAML and friends.
NB. Types are a kind of constraints.
Identity. It's often necessary in configuration to distinguish between two sub-sections that look the same and two sub-sections that designate the same exact object. Like, when configuring VMs with eg. disks: are they supposed to mount the same disk, or does each VM need a separate disk, that just has the same physical characteristics?
If you want to get crazy, you can push a dict into a list and operated on it but it gets tough at the second level. And don't get me started on if/else statements.