We construct non-trivial elements of order 2 in the homotopy groups π8j+1+ * Diff(D 6 , ∂) for * ≡ 1, 2 (mod 8), which are detected through the chainof the 'assembling homomorphism' (giving rise to the Gromoll filtration) and the alpha-invariant. These elements are constructed by means of Morlet's homotopy equivalence Diff(D 6 , ∂) Ω 7 (P L6/O6) and Toda brackets in P L6/O6. We also construct non-trivial elements of order 2 in π * P Lm for every m 6 and * ≡ 1, 2 (mod 8) which are detected by the alpha-invariant. As consequences, we (a) obtain non-trivial elements of order 2 in π * Diff(D m , ∂) for m 6 such that * + m ≡ 0, 1 (mod 8); (b) these elements remain non-trivial in π * 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 6 admits a metric with harmonic spinors; (e) there is no analogue of the odd-primary splitting of (P L/O) (p) for the prime 2; (f) for any bP8j+4-sphere (j 1) of order which divides 4, the corresponding element in π0Diff(D 8j+2 , ∂) lifts to π8j−4Diff(D 6 , ∂), that is, lies correspondingly deep down in the Gromoll filtration.