Zb. Maksic et B. Kovacevic, Spatial and electronic structure of highly basic organic molecules: Cyclopropeneimines and some related systems, J PHYS CH A, 103(33), 1999, pp. 6678-6684
It is shown, by utilizing a reliable model at the MP2 level of theory, that
the imino group attached to the cyclopropene moiety exhibits a high proton
affinity (PA). The reason behind the appreciable PA is identified as signi
ficant aromatization of the three-membered ring spurred by the protonation.
Further amplification of the PA can be achieved by NH;! substitutions at t
he CC endo double bond, since amino groups stimulate aromatization of the c
yclopropene fragment. Additionally, they release some of their lone pair el
ectron density thus contributing to a uniform distribution of the positive
charge over the entire molecular system. This effect is even more pronounce
d if the diaminoiminocyclopropene system is substituted by sizable alkyl gr
oups. The aromatic stabilization in the protonated 2,3-diaminocyclopropenei
mine, estimated by the corresponding homodesmic reaction, seems to be as hi
gh as 59.5 kcal/mol. Very potent organic bases can be obtained by designing
polycyclic systems possessing two or more cyclopropene fragments, where th
e aromatization occurs by the conjugation interaction transmitted through t
he Jr-electron network in a typical domino fashion. The highest PA value is
found, however, in a calicene-like structure embracing a quinoid six-membe
red ring and a cyclopropene moiety. Its proton affinity is well above the P
A value of the Schwesinger's proton sponge, which is known as the stongest
organic base so far. Importance of the iminocyclopropene motif in tayloring
of the strong organic superbases is stressed. The role of the intramolecul
ar hydrogen bending in some specific systems is briefly discussed.