A boolean is smaller, which is a relevant consideration for some workloads. For example, you may be pre-aggregating a large amount of data to serve a set of analytical queries which do not care about the associated timestamp. The smaller data type is more efficient both in storage and in query execution.
Additionally, there are situations where it is logical to store a boolean. For example, if the boolean denotes an outcome:
process_executed_at timestamp not null
process_succeeded boolean not null