Packing analysis in reactive crystals: the decomposition of bis(3,3,3-triphenylpropanoyl)peroxide in the solid state

Structure of ammonium p-toluenesulfonate

“…Rotation of ring B of o-diphenylbenzene shows an unusually steep well of 35kJmo1-1 at 45 ° and 90kJmo1-1 at 30 ° . The photocyclization process must involve simultaneous rotation of phenyl groups B and C with distortion of • studied byocompanngithe site of approximately 8.8 x 5.3 x4.4A revealed' by a packing calculation (Gavezzotti, 1987) with the observed interatomic distances, thermal parameters and the final difference map. The only symmetry constraint is that equal numbers of methyl groups must point in opposite directions to satisfy the centre of inversion.…”

J. Michael McBride at 65 − An Appreciation

“…25,40,41 Studies of TPPP and related systems made it clear that reaction-induced stress could be a controlling feature of solid-state reactivity. 42 Reasoning that repul- sive potentials vary much more rapidly with distance that attractive ones, Mike generalized this work and created a new classification scheme for understanding how a rigid environment can influence the rate of a single step reaction (Figure 5). Although most techniques for studying solid-state reactions cannot identify (much less distinguish) such influences, the exquisitely detailed information from radical pair EPR studies allows this in many instances.…”

“…Studies of TPPP and related systems made it clear that reaction-induced stress could be a controlling feature of solid-state reactivity . Reasoning that repulsive potentials vary much more rapidly with distance that attractive ones, Mike generalized this work and created a new classification scheme for understanding how a rigid environment can influence the rate of a single step reaction (Figure ).…”

Computational Prediction of the Enantioselectivity of a Solid-State Photoreaction

“…The first attempt to treat this situation computationally was made by Warshel and Shakked in 1975, who modeled solid-state excimer formation using an SCF-MO technique to describe the excited-state molecules and an empirical nonbonded exponential potential for intermolecular interactions with the rigid lattice neighbors . A subsequent approach used by Gavezzotti and co-workers, as well as by Ariel et al, begins with an X-ray crystal structure of the reactant and its nearest neighbors and distorts a central molecule in the cluster along a hypothetical reaction path while monitoring changes in its energy of interaction with the stationary lattice. No optimization is involved.…”