You can find the chance of getting a pair of doubles using combinations. Here's one way.
First, recall that a "combination" of $n$ things taken $k$ at a time is just a $k$-element subset of those things. The number of distinct combinations is a binomial coefficient, written (and often computed) as
$$\binom{n}{k} = \frac{n!}{(n-k)!k!}.$$
The key to this approach is to create an economical notation to describe the events of interest. To this end, note that the outcomes of $5$ independent rolls of a six-sided die correspond to six-element vectors whose entries count the number of appearances of each side. Specifically, when side $i$ appears $n_i$ times among those five rolls, entry $i$ in the vector is $n_i.$ For instance, if two threes appear along with one each of 1, 4, and 5, the vector would be $(1,0,2,1,1,0).$
Let the "pattern" of a vector be the counts of its entries. The pattern of the preceding vector is two zeros, three ones, and a two. We can write this pattern as a sequence of the counts $2, 3, 1, 0, 0, \ldots.$ (It's unnecessary to write the terminal zeros.)
Solve the problem in these steps.
Identify all patterns with two doubles. This is straightforward: they would be $0,1,2$ and $0,0,1,1.$ (What characterizes them is that these are sequences of natural numbers $k_0, k_1, k_2, \ldots$ for which $\sum_{i=0}^\infty i\,k_i = 5$ and $\sum_{i=2}^\infty k_i \ge 2.$ The first sum counts the dice while the second counts the outcomes appearing two or more times.)
Identify the number of ways each pattern could appear in a six-vector.
The pattern $0,1,2$ picks out two outcomes having doubles and, among the remaining $6-2 = 4$ outcomes, it picks out one more possibility. There are $\binom{6}{2}=15$ in the first case and $\binom{6-2}{1}=4$ in the other for a total of $15\times 4 = 60$ possibilities.
The pattern $0,0,1,1$ picks out one outcome with a double and another with a triple. There are $\binom{6}{1}=6$ ways for the first to occur and then $\binom{6-1}{1}=5$ more ways for the other to occur, for a total of $6\times 5 = 30$ possibilities.
Compute the chances of all these possible six-vectors $\mathbf n.$ They are given by the multinomial coefficients $$\binom{5}{\mathbf n} = \frac{5!}{n_1!n_2!\cdots n_6!},$$ each multiplied by the chance of any individual outcome; namely, $6^{-5}.$ Since these multinomial coefficients don't change when the elements of $\mathbb n$ are reordered, they depend only on the patterns, so there are only two values to work out: $$\binom{5}{(2,2,1,0,0,0)} = \frac{5!}{2!2!1!} = 30$$ and $$\binom{5}{(3,2,0,0,0,0)} = \frac{5!}{3!2!}=10.$$ (For convenience we usually don't write the zeros in the multinomial notation.)
Add the chances. We obtain $$\eqalign{\left(\binom{5}{(2,2,1)} \binom{6}{2} \binom{6-2}{1} + \binom{5}{(3,2)} \binom{6}{1}\binom{6-1}{1} \right)6^{-5} &= \frac{30(15)(4) + 10(6)(5)}{6^5} \\&= \frac{2100}{7776}.}$$
I have written the formulas in a way that suggests how they generalize to different patterns for different numbers of rolls for arbitrary-sided dice. Step 1 is the hard part in general: the rest are just straightforward calculation. Solving step 1 amounts to finding partitions with certain properties. This is a rich combinatorial subject but its analysis requires more advanced mathematics.