Chemistry of energetically activated cumulenes - from allene (H2CCCH2) to hexapentaene (H2CCCCCCH2).

During the last decade, experimental and theoretical studies on the unimolecular decomposition of cumulenes (H(2)C(n)H(2)) from propadiene (H(2)CCCH(2)) to hexapentaene (H(2)CCCCCCH(2)) have received considerable attention due to the importance of these carbon-bearing molecules in combustion flames, chemical vapor deposition processes, atmospheric chemistry, and the chemistry of the interstellar medium. Cumulenes and their substituted counterparts also have significant technical potential as elements for molecular machines (nanomechanics), molecular wires (nano-electronics), nonlinear optics, and molecular sensors. In this review, we present a systematic overview of the stability, formation, and unimolecular decomposition of chemically, photo-chemically, and thermally activated small to medium-sized cumulenes in extreme environments. By concentrating on reactions under gas phase thermal conditions (pyrolysis) and on molecular beam experiments conducted under single-collision conditions (crossed beam and photodissociation studies), a comprehensive picture on the unimolecular decomposition dynamics of cumulenes transpires.