The Protonation of Allene and Some Heteroallenes, a Computational Study

Abstract

Protonation of allene and seven heteroallenes, X = Y = Z, at the terminal and central positions has been studied computationally at the MP2/6-311+G**, B3LYP/6-31+G**, and G3 levels. In all but one case protonation at a terminal position is preferred thermodynamically. The exception is allene, where protonation at C2 giving allyl cation prevails by about 10 kcal/mol over end-protonation, which gives the 2-propenyl cation. In the heteroallenes, protonation at a terminal carbon is strongly favored, activated by electron donation from the other terminal atom. Transition states for identity proton-transfer reactions were found for 10 of the "end-to-end" proton transfers. When the transfer termini are heteroatoms these processes are barrier free. We found no first-order saddle point structures for "center-to-center" proton transfers. An estimate of DeltaH++ for an identity center-to-center proton transfer could be made only for the reaction between the allyl cation and allene; it is approximately 22 kcal/mol higher than DeltaH++ for the end-to-end proton transfer between the 2-propenyl cation and allene. First-order saddle points for the proton transfer from H3S+ to both C1 and C2 of allene were found. The difference in activation enthalpies is 9.9 kcal/mol favoring protonation at C1 in spite of the thermodynamic disadvantage. We infer that protonation of X = Y = Z at central atoms passes through transition states much like primary carbenium (nitrenium, oxenium) cations, poorly conjugated with the attached vinylic or heterovinylic group. Several other processes following upon center protonation were studied and are discussed in the text, special attention being given to comparison of open and cyclic isomers.