Theoretical study of reactant activation in 1,3-dipolar cycloadditions of cyclic nitrones to free and Pt-bound nitriles.

[reaction: see text] 1,3-Dipolar cycloaddition of the cyclic nitrones CH2(CH2)2CH=NO (N1), CH2CH2OCH=NO (N2), CH2-OCH2CH=NO (N3), and O(CH2)2CH=NO (N4) to organonitriles, RCN-both free (R = CH(3), CF(3)) and ligated to Pt(II) and Pt(IV) (in the complexes trans-[PtCl(2)(NCCH(3))(2)] (1) and trans-[PtCl(4)(NCCH(3))(2)] (2))-was investigated extensively by theoretical methods at different levels of theory. The effectiveness of two types of dipolarophile activation (by introducing a strong electron-acceptor group R and by coordination to a metal center) was analyzed and compared. The influence of factors such as the nature of the cyclic nitrone and the nature of the solvent on the reactions was also studied. The reactivity of dipoles and dipolarophiles increases along the series N4 < N1 approximately N3 < N2 and CH(3)CN < CF(3)CN < 1 < 2; the latter demonstrates that the coordination of RCN to a Pt center provides an even higher activation effect upon cycloaddition in comparison with the introduction of a strong electron-acceptor group R such as CF(3). A higher reactivity of the cyclic dipole N1 in comparison with acyclic nitrones (e.g., CH(3)CH=N(CH(3))O) is interpreted to be a result of its exclusive existence in a more strained and hence more reactive E- rather than Z-configuration. The activation and reaction energies have been calculated at different basis sets and levels of theory, up to MP4(SDTQ), CCSD(T), and CBS-Q. The activation energies are weakly sensitive to a change of the correlated methods. The consideration of the solvent effects results in the increase of the activation barriers, and such enhancement is less pronounced for the nonpolar or low polar solvents. The cycloadditions to CH(3)CN and CF(3)CN were found to be nearly synchronous, but these reactions involving 1 and 2 are clearly asynchronous. Moreover, the reaction of N2 with 2 proceeds via a very early acyclic transition state, while for all other reactions the transition states have a cyclic nature.