The reaction of ground state carbon atoms, C(P-3(j)), with dimethylacetylene, H3CCCCH3, was studied at three collision energies between 21.2 and 36.9 kJmol(-1) employing the crossed molecular beam approach, Our experiments were combined with ab initio and RRKM calculations. It is found that the reaction is barrierless via a loose, early transition stare located at the centrifugal barrier following indirect scattering dynamics through a,complex. C(P-3(j)) attacks the pi system of the dimethylacetylene molecule to form a dimethylclopropenylidene intermediate either in one step via an addition to C1 and C2 of the acetylenic bond or through an addition to only one carbon atom. to give a short-lived cis/trans dimethylpropenediylidene intermediates followed by ring closure. The cyclic intermediate ring opens to a linear dimethylpropargylene radical which rotates almost parallel to the total angular momentum vector J. This complex fragments to atomic hydrogen and a linear 1-methylbutatrienyl radical, H2CCCCCH3(X(2)A"), via a tight exit transition state located about 18 kJmol(-1) above the separated products. The experimentally determined exothermicity of 190+/-25 kJmol(-1) is in strong agreement with our calculated data of 180+/-10 kJmol(-1). The explicit verification of the carbon versus hydrogen exchange pathway together with the first identification of the H2CCCCCH3 radical represents a third pathway to form chain C5H5 radicals in the reactions of C(P-3(j)) with C4H6 isomers under single collision conditions. Previous experiments of atomic carbon with the 1,3-butadiene isomer verified the formation;,of 1- and 3-vinylpropargyl radicals, HCCCHC2H3(X(2)A"), and H2CCCC2H3(X(2)A"). respectively. In high-density environments; such as combustion flames and circumstellar envelopes of carbon stars, these linear isomers can undergo collision-induced ring closure(s) and/or H atom migration(s) which can lead to the cyclopentadienyl radical. The latter is thought to be a crucial reactive intermediate in soot formation and possibly in the production of polycyclic aromatic hydrocarbon molecules in outflow of carbon stars. Likewise, a H atom catalyzed isomerization can interconvert the 3-vinylpropargyl and the 1-methylbutatrienyl radical.