The
poorly understood mode of activation and catalysis of bidentate
iodine(III)-based halogen donors have been quantitatively explored
in detail by means of state-of-the-art computational methods. To this
end, the uncatalyzed Diels–Alder cycloaddition reaction between
cyclohexadiene and methyl vinyl ketone is compared to the analogous
process mediated by a bidentate iodine(III)-organocatalyst and by
related, highly active iodine(I) species. It is found that the bidentate
iodine(III)-catalyst accelerates the cycloaddition by lowering the
reaction barrier up to 10 kcal mol
–1
compared to
the parent uncatalyzed reaction. Our quantitative analyses reveal
that the origin of the catalysis is found in a significant reduction
of the steric (Pauli) repulsion between the diene and dienophile,
which originates from both a more asynchronous reaction mode and a
significant polarization of the π-system of the dienophile away
from the incoming diene. Notably, the activity of the iodine(III)-catalyst
can be further enhanced by increasing the electrophilic nature of
the system. Thus, novel systems are designed whose activity actually
surpasses that of strong Lewis acids such as BF
3
.
The influence of the nature of the acid/base pairs on the reactivity of geminal frustrated Lewis pairs (FLPs) (Me2E‐CH2‐E′Ph2) has been computationally explored within the density functional theory framework. To this end, the dihydrogen‐activation reaction, one of the most representative processes in the chemistry of FLPs, has been selected. It is found that the activation barrier of this transformation as well as the geometry of the corresponding transition states strongly depend on the nature of the E/E′ atoms (E=Group 15 element, E′=Group 13 element) in the sense that lower barriers are associated with earlier transition states. Our calculations identify the geminal N/Al FLP as the most active system for the activation of dihydrogen. Moreover, the barrier height can be further reduced by replacing the phenyl group attached to the acidic atom by C6F5 or 3,5‐(CF3)2C6H3 (Fxyl) groups. The physical factors controlling the computed reactivity trends are quantitatively described in detail by means of the activation strain model of reactivity combined with the energy decomposition analysis method.
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