I am not sure whether the problem you have is to show that n does not divide 2^n-1 ( that is they are relatively prime) or to show that if 2^n-1 is prime than n is prime ( in which case i am not sure that the latter even holds). However, if it is the former here is another approach to this problem: Suppose the contrary: that is let 2^n-1 be a prime number and n a number not relatively prime to it. Now, let p_1 be a prime divisor of n, and let k be the smallest positive integer for which p_1 divides 2^k-1. Now from Fermat's little theorem we would get that p_1 is also a factor of 2^{p_1-1}-1. Hence k\leq p_1-1<p_1.
Now your task is to prove that q divides n. Assume the contrary, by expressing n=hq+r.
I will stop here before i get in trouble from PF Moderators!
Hope this was helpful.