This paper describes how the rates of 5-exo-ring closures Of Unsaturated iminyl radicals to pyrrolomethyl radicals respond to substituents in the pentenyl chain and at the C=N bond. Benzyl- and acyl oxime esters, as well as dioxime oxalates, were identified as Suitable iminyl radical sources for electron paramagnetic resonance (EPR) spectroscopy. Pentenyliminyl radicals with aryl substituents at their C=N bonds, and one with an alkyl substituent at its C=N bond,were Studied in Solution by steady-state Continuous wave EPR spectroscopy. All the pentenyliminyls selectively ring closed in the 5-exo-mode rather than the 6-endo-mode. EPR monitoring of the decay of the 2,2-dimethyl-1-phenylpent-4-enyliminyl radical showed that it underwent bimolecular combination at about the diffusion controlled limit (2kt similar to 3 x 10(8) M-1 s(-1) at 245 K). The rate constant for 5-exo-ring Closure of phenylpentenyliminyl (8.8 x 10(3) s(-1) at 300 K) was a factor of 25 smaller than the rate constant for hex-5-enyl radical cyclization. The rate of cyclization was slower for an iminyl having a Me group at the site of 5-exo-cyclization but faster for an iminyl with an Et substituent at the terminus of the C=C double bond. Surprisingly, the 2,2-dimethyl-1-phenylpent-4-enyliminyl radical, with a bismethyl group in its pentertyl chain, ring closed more slowly than the unsubstituted analogue. DFT computations were in accord with this inverse gem-dimethyl effect and Suggested it resulted from steric interaction of the Ph and bis-Me groups which forced the aromatic ring out of the plane of the imine moiety. To check on the role of the Ph substituent, pentenyliminyls lacking this group were sought. A pentenyliminyl radical with an alkyl group in place of the Ph group, and a single Me group in its pentenyl chain, was generated by means of an unsymmetrical dioxime oxalate precursor. The k(c) for this species wits a factor of 2.5 larger than k(c) for the original pentenyliminyl, suggesting that the normal positive gem-dimethyl effect does operate for pentenyliminyls lacking the aromatic substituent at the C=N bond. DFT Computations also successfully reproduced this trend for model iminyls. It appears that for alkenyliminyl radicals positive or negative gem-dimethyl effects on the cyclization can be induced by appropriate choice of the second substituent on the C=N bond.