We construct non-trivial elements of order 2 in the homotopy groups $\pi_{8j+1+*} Diff(D^6,\partial)$, for * congruent 1 or 2 modulo 8, which are detected by the "assembling homomorphism" (giving rise to the Gromoll filtration), followed by the alpha-invariant in $KO_*=Z/2$. These elements are constructed by means of Morlet's homotopy equivalence between $Diff(D^6,\partial)$ and $\Omega^7(PL_6/O_6)$, and Toda brackets in $PL_6/O_6$. We also construct non-trivial elements of order 2 in $\pi_* PL_m$ for every m greater or equal to 6 and * congruent to 1 or 2 modulo 8, which are detected by the alpha-invariant. As consequences, we (a) obtain non-trivial elements of order 2 in $\pi_* Diff(D^m,\partial)$ for m greater or equal to 6, and * + m congruent 0 or 1 modulo 8; (b) these elements remain non-trivial in $\pi_* Diff(M)$ where M is a closed spin manifold of the same dimension m and * > 0; (c) they act non-trivially on the corresponding homotopy group of the space of metrics of positive scalar curvature of such an M; in particular these homotopy groups are all non-trivial. The same applies to all other diffeomorphism invariant metrics of positive curvature, like the space of metrics of positive sectional curvature, or the space of metrics of positive Ricci curvature, provided they are non-empty. Further consequences are: (d) any closed spin manifold of dimension m greater or equal to 6 admits a metric with harmonic spinors; (e) there is no analogue of the odd-primary splitting of $(PL/O)_{(p)}$ for the prime 2; (f) for any $bP_{8j+4}$-sphere (where j > 0) of order which divides 4, the corresponding element in $\pi_0 Diff(D^{8j+2},\partial)$ lifts to $\pi_{8j-4} Diff(D^6,\partial)$, i.e., lies correspondingly deep down in the Gromoll filtration.