I would like to prove (or disprove) the following statement: $$ \sum_{n=0}^\infty \left[\frac{{}_2{\rm F}_1\left(\frac{1}{2},\frac{1-n}{2};\frac{3}{2};1\right)}{n!}\right] = \frac{\pi}{2} \left[ \sum_{a=0}^\infty \frac{1}{4^a (a!)^2} + \frac{1}{2} \sum_{b=0}^\infty \frac{\left(\frac{1}{2}\right)^{2b}}{\Gamma\left(b+\frac{3}{2}\right)^2}\right] $$ also can be seen as $$ \sum_{n=0}^\infty \left[\frac{{}_2{\rm F}_1\left(\frac{1}{2},\frac{1-n}{2};\frac{3}{2};1\right)}{n!}\right] = \frac{\pi}{2} \bigg[ I_0(1) + L_0(1) \bigg] $$ Where $I_0(1)$ is the modified bessel function of the first kind and $L_0(1)$ is the modified struve function.
Major brownie points on the line here!
I'll prove a generalization of the second expression. We first recall Gauss's theorem $\displaystyle _2F_1(a,b;c;1)=\frac{\Gamma(c)\Gamma(c-a-b)}{\Gamma(c-a)\Gamma(c-b)}$ which implies $$_2F_1\left(\frac{1}{2},\frac{1-n}{2};\frac{3}{2};1\right) =\frac{\Gamma(3/2)\Gamma((1+n)/2)}{\Gamma(1)\Gamma(1+n/2)}=\frac{\sqrt{\pi}}{2}\frac{\Gamma(1/2+n/2)}{\Gamma(1+n/2)}.$$ Furthermore, applying the duplication formula $\Gamma(z)\Gamma(z+1/2)=2^{1-2z}\sqrt{\pi}\,\Gamma(2z)$ for $z=1/2+n/2$ yields $\Gamma(1/2+n/2)\Gamma(1+n/2)=2^{-n}\sqrt{\pi}\,n!$. Consequently the hypergeometric function further rewrites to $$\frac{\sqrt{\pi}}{2}\frac{\Gamma(1/2+n/2)}{\Gamma(1+n/2)}=\frac{\pi}{2}\frac{2^{-n}n!}{\Gamma(1+n/2)^2},$$ and we may write the equality
$$\sum_{n=0}^\infty\,_2F_1\left(\frac{1}{2},\frac{1-n}{2};\frac{3}{2};1\right)\frac{x^n}{n!} = \frac{\pi}{2}\sum_{n=0}^\infty \frac{(x/2)^n}{\Gamma(1+n/2)^2}.$$
On the RHS, we recall that the functions involved have series definitions $$I_0(x)=\sum_{n=0}^\infty \frac{(x/2)^{2n}}{\Gamma(1+n)^2},\quad L_0(x)=\sum_{n=0}^\infty \frac{(x/2)^{2n+1}}{\Gamma(3/2+n)^2}.$$ But, save for a factor of $\pi/2$, these are just the even and odd parts respectively of the summation just displayed. Consequently we conclude
$$\sum_{n=0}^\infty\,_2F_1\left(\frac{1}{2},\frac{1-n}{2};\frac{3}{2};1\right)\frac{x^n}{n!}=\frac{\pi}{2}\left(I_0(x)+L_0(x)\right).$$ Taking $x=1$ yields the identity of interest.