Concep: Let $f$ be a function, which means $$x_1=x_2\Rightarrow f(x_1)=f(x_2)$$
But note that if $f(x_1)=f(x_2)$, then $x_1=x_2$ is one of the possibility, among perhaps many possibilities if the function is not injective
Now Given $\tan^{-1}(2x)+\tan^{-1}(3x)=\frac{\pi}{4}$, taking $\tan$ of both sides(since $\tan$ is a function),we get
$$\frac{2x+3x}{1-2x.3x}=1$$
which after simplification gives $x=\frac16,-1$. Taking $x=\frac16$, we want to find what is $\tan^{-1}\frac13+\tan^{-1}\frac12$. For that let us take $\tan^{-1}\frac13=\alpha,\tan^{-1}\frac12=\beta$, which is equal to $\tan\alpha=\frac13,and \tan\beta=\frac12$, where $\alpha,\beta$ being principal values belongs to $(-\frac{\pi}2,\frac{\pi}2)$, which means $\alpha+\beta\in(-\pi,\pi)$. Now we know $$\tan(\alpha+\beta)=\frac{\tan\alpha+\tan\beta}{1-\tan\alpha\tan\beta}$$ which implies $$\tan(\alpha+\beta)=\frac{\frac13+\frac12}{1-\frac13\frac12}=1$$ Hence $$\alpha+\beta=\tan^{-1}1=\frac{\pi}4$$ or $$\tan^{-1}\frac13+tan^{-1}\frac12=\frac{\pi}4$$ and $x=\frac16$ becomes a root of the above equation
Now take $x=-1$, then the lhs of the equation becomes $$\tan^{-1}(-2)+\tan^{-1}(-3)$$ which is a negative angle $-\frac{3\pi}{4}$ , which can not be a positive number $\frac{\pi}{4}$.