For Question 2, there are only two kinds of such examples: the case where $G$ is commutative and even-dimensional, and the case where all simple factors of $G$ come in isomorphic pairs. (In the former case, the action of $G$ is trivial, so we may arbitrarily put a complex structure on $\DeclareMathOperator\Lie{Lie}\Lie(G)$. In the latter case, for each pair of isomorphic simple factors $G_1$ and $G_2$, given any choice of $G$-equivariant isomorphism $J_{12} : \Lie(G_1) \to \Lie(G_2)$, we may (uniquely) choose $J_{21} = -J_{12}^{-1}$, and then piece these various maps together to make $J$.)
If we are not in either of those cases, then there is some simple factor of $G$ whose Lie algebra is preserved by $J$, so it suffices to consider $G$ (compact and) simple. Then the adjoint representation is absolutely irreducible, so there is at most one $G$-invariant bilinear form, up to scalars. The Killing form $\kappa$ is a non-$0$, real-valued such form, and $\kappa_J \mathrel{:=} \kappa(J\cdot, \cdot)$ is another, so $\kappa_J$ equals $\lambda\kappa$ for some real scalar $\lambda$. But then $-\kappa = \kappa_{J^2}$ equals $\lambda\kappa_J = \lambda^2\kappa$, so $\lambda^2$ equals $-1$, which is a contradiction.
In the direction of Question 1 (though not answering it), the same argument ruling out complex-type adjoint representations works for any semisimple, linear Lie group $G$, as long as its simple factors are absolutely simple, and do not come in isomorphic pairs. A simple factor may instead be (the group of $\mathbb R$-points of) the restriction of scalars of that marvellous combination of adjectives, a simple, complex algebraic group, in which case, as @MikhailBorovoi points out in a comment, the adjoint representation on the corresponding factor of the Lie algebra will be of complex type.