Your both methods have some mistake.
Method 1 -
Getting 2 on first number and any other number on second except 5. But 2 can be on second die also. So multiply cases with 2.
$2 \left(\frac16 \times \frac46\right)$
= $\left(\frac13 \times \frac23\right)$
= $\left(\frac29\right)$
Similarly for getting 5 on first number and any other number on second except 2. But 5 can be on second die also. So multiply cases with 2.
$2 \left(\frac16 \times \frac46\right)$
= $\left(\frac13 \times \frac23\right)$
= $\left(\frac29\right)$
Case with 2 on both dice or 5 on both dice.
$\left(\frac16 \times \frac16 + \frac16 \times \frac16\right)$
= $\left(\frac1{36} + \frac1{36}\right)$
= $\left(\frac2{36}\right)$
Case with 2 on first die and 5 on second or vice versa.
$\frac16 \times \frac16 + \frac16 \times \frac16$
= $\left(\frac1{36} + \frac1{36}\right)$
= $\left(\frac2{36}\right)$
Combining these,
$\left(\frac29 + \frac29 + \frac2{36} + \frac2{36}\right)$
= $\left(\frac{20}{36}\right)$
Method 2 -
21, 22, 23, 24, 25, 26, 12, 32, 42, 52, 62, 15, 35, 45, 55, 65, 51, 53, 54, 56 = 20 cases.