On the Lack of Conjugation Stabilization in Polyynes (Polyacetylenes)

Abstract

By analogy to conjugated polyenes, conjugative stabilization of polyynes with the -CC-CC- group might be expected to be substantial. On the contrary, consistent with our recent report of a surprising lack of conjugative stabilization in butadiyne, we find by G3(MP2) calculations and by comparisons with available experimental data from these and other laboratories that the ground-state stabilization of conjugated polyynes is in fact quite small, amounting to <1 kcal mol(-)(1). By similar calculations, the 2,4-pentadiyn-1-yl radical shows no enhanced stabilization relative to 2-propyn-1-yl radical, despite the potential stabilization of the odd electron by two conjugated triple bonds and unlike the behavior of 2,4-pentadien-1-yl radical. The thermochemistry of straight-chain alkynes and polyynes is very self-consistent. Enthalpies of hydrogenation, leading to enthalpies of formation, are predictable with a high degree of accuracy (absolute mean deviation = +/-0.39 kcal mol(-)(1) vs theoretical values and +/-0.52 vs experimental) from three molecular structure enthalpies and one conjugation stabilization parameter.