100 rolls of a fair die can be considered as a multinomial distribution. For simplicity, we will consider 3 categories: a roll of a 1, a roll of a 2, and everything else.
Let $\pi_i$ be the probability for each of the three categories. The density is
$$ \dfrac{\Gamma(101)}{\Gamma(a+1) \Gamma(b+1)\Gamma(101-a-b)} \pi_1^a \pi_2^b \pi_3^{100-a-b} = \dfrac{100!}{a!b!(100-a-b)!} \pi_1^a \pi_2^b \pi_3^{100-a-b} $$
You will notice that is is very similar to what you have posted. The probabilities for each category are 1/6, 1/6, and 4/6 respectively. Note, the probabilities for each category must sum to 1.
As to your point
I am confused whether $\frac{1}{6}^b$ should be used or $\frac{1}{5}^b.$
Why would you think the probability of rolling a 2 is 1/5?