The reaction dynamics to form the 1-cyano-1-methylallene isomer CNCH3CCCH2 in its (1)A' ground state via the radical-closed shell reaction of the cyano radical CN(X (2)Sigma(+)) with dimethylacetylene CH3CCCH3 (X (1)A(1)') are unraveled in a crossed molecular beam experiment at a collision energy of 20.8 kJ mol(-1) together with state-of-the-art electronic structure and Rice-Ramsperger-Kassel-Marcus (RRKM) calculations. Forward convolution fitting of the laboratory angular distribution together with the time-of-flight spectra verify that the reaction is indirect and proceeds by addition of the CN radical to the pi orbital to form a cis/trans CH3CNC=CCH3 radical intermediate. This decomposes via a rather lose exit transition state located only 6-7 kJ mol(-1) above the products to CNCH3CCCH2 and atomic hydrogen. The best fit of the center-of-mass angular distribution is forward-backward symmetric and peaks at pi/2 documenting that the fragmenting intermediate holds a lifetime longer than its rotational period. Further, the hydrogen atom leaves almost perpendicular to the C5H5N plane resulting in sideways scattering. This finding, together with low frequency bending and wagging modes, strongly support our electronic structure calculations showing a H-C-C angle of about 106.5 degrees in the exit transition state. The experimentally determined reaction exothermicity of 90 +/- 20 kJ mol(-1) is consistent with the theoretical value, 80.4 kJ mol(-1). Unfavorable kinematics prevent us from observing the CN versus CH3 exchange channel, even though our RRKM calculations suggest that this pathway is more important. Since the title reaction is barrierless and exothermic, and the exit transition state is well below the energy of the reactants, this process might be involved in the formation of unsaturated nitriles even in the coldest interstellar environments such as dark, molecular clouds and the saturnian satellite Titan.