In python lists and dictionaries are distinct types. PHP has the one type to rule them all the associative array.
I think what you want to do above translates into a list of dictionaries in python, like this
x = [ dict(Letter=chr(i)) for i in range(ord('a'),ord('f')) ]
If you try this in the interpreter
>>> x = [ dict(Letter=chr(i)) for i in range(ord('a'),ord('f')) ]
>>> x
[{'Letter': 'a'}, {'Letter': 'b'}, {'Letter': 'c'}, {'Letter': 'd'}, {'Letter': 'e'}]
>>> x[0]
{'Letter': 'a'}
>>> x[1]
{'Letter': 'b'}
>>> x[1]['Letter']
'b'
>>>
Or if you prefer it written out in full without a list comprehension
x = []
for c in range(ord('a'),ord('f')):
d = { 'Letter': chr(c) }
x.append(d)