Heh, so in Python it's possible to overload operators in the context of objects.
I bet it would be possible to overload tabs to do the same thing as colons inside a context manager, but that's pure speculation.
You can define what happens for an object when an operator is applied (like +, /, or -) so that you can obj+obj. I wonder if there's a way to override "tab" such that it acts like a ":", but from inside the language (this is trivial if you edit the language itself like you suggest). Thinking about it more, I'm guessing not since ":" isn't an operator and this doesn't have a corresponding __operator__ function.
If Python has anything like Perl's source code filters, then anything's up for grabs, but Perl is kind of weird in a way that Python was specifically designed not to be. Or at least Python 1 was. Things may have changed in the intervening couple of decades.
If it's just plain overloading, then whitespace is probably off the table. Spaces, even required spaces, aren't so much syntax as they are structure. You could argue that the curly braces of some other languages are more syntactic than Python's whitespace, because it's actually Python's magic colon and the first unindented line (lack of whitespace!) that serve that specific syntactic purpose.
Examples of Perl's source code filters range from turning a program into binary representation of the syntax tree and still having it be executable, to new syntax, to writing programs entirely in Latin or something that looks almost but not entirely unlike it, anyway.
IIRC, Python handles whitespace indentation by having the tokenizer convert them to INDENT/DEDENT tokens. The grammar can then handle them equivalently to a curly brace language.