Odd [n]Cumulenes (n = 3, 5, 7, 9): Synthesis, Characterization, and Reactivity.

Abstract

In comparison to the omnipresent two- and three-dimensional allotropes of carbon, namely, graphite and diamond (as well as recent entries graphene, carbon nanotubes, and fullerenes), a detailed understanding of the one-dimensional carbon allotrope carbyne is not well established, and even the existence of carbyne has been a matter of controversy over the past decades. Composed of sp-hybridized carbon, carbyne could potentially exist in two forms, either as a polyyne (alternating single and triple bonds, expected to show a semiconducting behavior) or as a cumulene (all carbon atoms are connected via double bonds, predicted to show metallic behavior). Although a number of publications are available on the hypothetical structure and properties of carbyne, specific knowledge about its physical and spectroscopic characteristics is still unclear. In order to predict the properties of carbyne, the synthesis and study of model compounds, namely, polyynes and cumulenes, has been a promising avenue. The synthesis of polyynes has been extensively explored in the last decades, culminating with the isolation of a polyyne with 22 acetylene units, which allows extrapolation to the properties of carbyne. Extended cumulenes, on the other hand, have remained much less well-known, and specific studies of properties versus molecular length are quite limited. A limiting factor to the study of [n]cumulenes has been their dramatically increased reactivity, especially in comparison to polyynes of comparable length. For example, most known [7]cumulenes can only be handled in solution, while the polyynes of equivalent length (i.e., a triyne with three acetylene units) are quite stable. [9]Cumulenes are the longest derivatives studied to date. In this Account, we describe our efforts to design and synthesize odd [n]cumulenes (i.e., n = 3, 5, 7, 9) that are sufficiently persistent under ambient conditions to allow in depth characterization of physical and spectral properties. This goal has been achieved through modification of the end-capping groups by increasing the steric bulk and thereby shielding the reactive cumulene framework to provide stable [7]- and [9]cumulenes. An alternative route to stabilization is accomplished via encapsulation of the cumulene skeleton in a macrocycle, that is, formation of cumulene rotaxanes. The new sterically encumbered cumulenic products are reasonably stable under normal laboratory conditions, although some readily undergo cycloaddition reactions to give interesting products. We have explored preliminary trends for the reactivity of long [n]cumulenes. Finally, trends in the series of [n]cumulene model compounds are now discernible, including a thorough consideration of bond length alternation (BLA) in long [n]cumulenes using X-ray crystallographic analyses, as well as electronic properties via UV-vis spectroscopy and cyclic voltammetry.