The question is not about 2's complement of -539, rather what is the 2's complement representation of -539.
In 2's complement representation negative numbers are represented as 2's complement of its absolute value while positive numbers are representes as they are.
So, $(-539)_{10} = 2's(001000011011)_2 = (110111100101)_2 = (DE5)_{16}$.
For $539$, answer would have been $(001000011011)_2 = (21B)_{16}$