Technically you can use $\frac{5\pi}{6}$ as one of the bounds of $\theta,$
but you have to beware of several pitfalls.
One question is about the substitution. Just looking at the antiderivative
(not the bounds) for the moment, the immediate result of the substitution
$x = \sin\theta$ is
$$
\int \frac{\sin \theta}{\sqrt{1 - \sin^2\theta}}\, \cos\theta \,\mathrm d\theta,
$$
which simplifies to
$$
\int \frac{\sin \theta}{\sqrt{\cos^2\theta}}\, \cos\theta \, \mathrm d\theta.
$$
We usually further simplify this to
$$ \int \sin \theta \, \mathrm d\theta, $$
but that simplification assumes that $\sqrt{\cos^2\theta} = \cos\theta,$
which is true only if $\cos\theta \geq 0,$
which is not true when $\frac\pi2 < \theta < \frac{3\pi}{2}.$
You can still bound the integral by values of $\theta$ that are not in the interval
$\left[-\frac\pi2,\frac\pi2\right],$
as explained in this answer,
but you have to be careful that you are actually using the correct substitution.
A substitution that works for all $\theta$ is
$$
\int \frac{x}{\sqrt{1-x^2}}\,\mathrm dx
= \int \sin \theta \operatorname{sgn}(\cos\theta)\, \mathrm d\theta,
$$
where
$$
\operatorname{sgn}(y) = \begin{cases}1 & y > 0,\\0 & y = 0,\\-1 & y < 0.\end{cases}
$$
For example, the following is a valid substitution:
\begin{align}
\int_0^{1/2} \frac{x}{\sqrt{1-x^2}}\,\mathrm dx
&= \int_\pi^{5\pi/6} \sin \theta \operatorname{sgn}(\cos\theta)\, \mathrm d\theta\\
&= \int_\pi^{5\pi/6} -\sin \theta \, \mathrm d\theta & \cos\theta < 0\\
&= \bigg[ \cos \theta \bigg]_\pi^{5\pi/6}\\
&= \left(-\frac{\sqrt3}2\right) - (-1)\\
&= 1 - \frac{\sqrt3}2,
\end{align}
which is the correct answer.
Note that when $-\pi \leq \theta \leq \frac{5\pi}{6}$ we have
$0 \leq x \leq \frac12,$ and the substitution $x = \sin\theta$
really does relate each value of $\theta$ to one value of $x$ in the original interval of integration.
If you instead integrate from $0$ to $\frac{5\pi}{6}$
things start to get a little weird:
as $\theta$ goes from $0$ to $\frac{5\pi}{6}$,
$x$ goes from $0$ to $1$ and then back down to $\frac12.$
If you're careful, the integral over $\theta$ from $\frac\pi2$ to $\frac{5\pi}{6}$
will exactly cancel the integral from $\frac{\pi}{6}$ to $\frac\pi2$,
and you'll end up with exactly what you would have had if you had just
integrated over $\theta$ from $0$ to $\frac{\pi}{6}$ in the first place.
But you do need to be careful, since $\cos\theta$ changes sign over the
interval of integration.