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The chemical dynamics to synthesize the 2,4-pentadiynyl-1 radical, HCCCCCH2(X2B1), via the neutral−neutral reaction of dicarbon with methylacetylene, was examined in a crossed molecular beams experiment at a collision energy of 37.6 kJ mol-1. The laboratory angular distribution and time-of-flight spectra of the 2,4-pentadiynyl-1 radical and its fragmentation patterns were recorded at m/z = 63−60 and m/z = 51−48. Our findings suggest that the reaction dynamics are indirect and dictated by an initial attack of the dicarbon molecule to the π electron density of the methylacetylene molecule to form cyclic collision complexes. The latter ultimately rearranged via ring opening to methyldiacetylene, CH3−C≡C−C≡C−H. This structure decomposed via atomic hydrogen emission to the 2,4-pentadiynyl-1 radical; here, the hydrogen atom was found to be emitted almost parallel to the total angular momentum as suggested by the experimentally observed sideways scattering. The overall reaction was strongly exoergic by 182 ± 10 kJ mol-1. The identification of the resonance-stabilized free 2,4-pentadiynyl-1 radical represents a solid background for the title reaction to be included into more refined reaction networks modeling the chemistry of circumstellar envelopes and also of sooting combustion flames. [ABSTRACT FROM AUTHOR]