Mono-Cp titanium coordination compounds bearing monoanionic ligands derived from stable nitroxyl radicals have been synthesized by two methods: (i) trapping of CpTi(III) species with the stable nitroxyl radical TEMPO (2,2,6,6-tetramethylpiperidine-N-oxyl) to provide Cp′TiCl2(TEMPO) (Cp′ = Cp (1) and Cp* (2)) and (ii) salt metathesis of Ti(IV) halides with a nitroxide anion generated by the in situ methylation of tert-butyl-α-phenylnitrone. Alkylation of these complexes with MeLi or MeMgBr furnishes Cp*TiMe2(TEMPO) (3) and Cp′TiMe2(ON(tBu)(CHMePh)) (Cp′ = Cp(4) and Cp* (5)). The molecular structure of 2 has been determined by X-ray crystallography to reveal a monoanionic η1-TEMPO ligated to titanium. Complexes 3 and 4 activated with iprAFPB (2,6,-diisopropyl-N,N-dimethylanilinium tetrakis(pentafluorophenyl)borate) efficiently copolymerize ethylene and 1-hexene to provide copolymers having higher 1-hexene contents and higher productivities than the related Cp*Ti(CH2Ph)3 under identical conditions. Comparison of structural and electronic features as well as the ethylene/1-hexene copolymerization behavior of 3 and 4 with the constrained geometry catalyst [MeSi2(η5-Me4Cp)(η1-N-tBu)]T iMe2 (6) provides insights into factors governing high comonomer incorporation by mono-Cp titanium complexes.