Rearrangement of azirine intermediates to nitriles: Theoretical study of cleavage of 3,4-dihydro-1aH-azirine[2,3-c]pyrrol-2-one to cyanoketene-formaldimine complex

Journal of Computational Chemistry

Volumn 19, Issue 8, 1998, Pages 912-922

  Calvo Losada, Saturnino ^a   Quirante, José Joaquín ^a   Suárez, Dimas ^b   Sordo, Tomás Luis ^b  

^a UNIVERSITY OF MÁLAGA   (Spain)

^b UNIVERSITY OF OVIEDO   (Spain)

Author keywords

Ab initio calculations; Bicyclic azirine intermediates; Coarctate transition structures; DFT calculations; Ring cleavage

Indexed keywords

EID: 0001162038     PISSN: 01928651     EISSN: None     Source Type: Journal    
DOI: 10.1002/(SICI)1096-987X(199806)19:8<912::AID-JCC10>3.0.CO;2-9     Document Type: Article

References (48)

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40. 20 Thus, a (3, + 1) critical point [local depletion of ρ(r + (Combining right arrow above sign))] on the valence shell of the C3 atom, is found to be aligned with a (3, - 1) critical point [secondary local concentration of ρ(r + (Combining right arrow above sign))] on the valence shell of the N7 atom.
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43. c) - B)], where the A and B parameters were obtained by a least-square fitting procedure assigning n = 1 to methylamine, n = 2 to formaldimine, and n = 3 for hydrogen cyanide at the MP2/6-31G*; and B3LYP/6-31C* levels.
44. (a) ∇H and ∇G ab initio values were computed using MP2(FC)/6-31G* frequencies and electronic energies approximated in an additive fashion as follows: E[QCISD(T)/ -311 + G(3df,2p)] ≈ E[QCISD(T)/6-31G*] + E[MP2/6-311 + (3df,2p)] - E[MP2/6-31G*]. See L. A. Curtiss, P. C. Redfem, B. J. Smith, and L. Radom, J. Chem. Phys., 104, 5148 (1996);
45. (b) ΔH and ΔG DFT values were computed using the B3LYP/6-31G* frequencies and B3LYP/6-311 + G(3df,2p)//B3LYP/6-31G* electronic energies.
46. vib(T) were scaled using the recommended frequency scaling factors: A. P. Scott and L. Radom, J. Phys. Chem., 100, 16502 (1996).
47. Although the results of the IRC calculations presented in Figure 2 could suggest some discontinuity near the TS, we checked that no HOMO-LUMO crossing takes place during the evolution of the system. A CISD/6-31G*//MP2/6-31G* single-point calculation at the TS also confirms that the singlet wave function is absolutely dominated by the HF reference wave function.
48. 8 was located on the B3LYP/6-31G* PES. This intermediate is characterized by a C(ketene)-N(imine) bond distance of 1.608 Å and a notable charge transfer of 0.43 e from formaldimine to cyanoketene. However, only 0.6 kcal/mol at the B3LYP/6-31G* level is required to produce fragmentation of the zwitterion passing through the corresponding TS to yield the cyanoketene-formaldimine planar van der Waals cis-complex (0.5 kcal/mol more stable than the zwitterion). The inclusion of ZPVE provokes the disappearance of the zwitterionic intermediate on the PES given that the TS for fragmentation turns out to be 0.1 kcal/mol more stable than the zwitterion.