Table . Comparison of HF-EPR data for compounds 13a, 13d, and 13e with other axially coordinated Mn(III) tetrapyrrole analogues. E is given in the same sign as D (TPFC = 5,10,15-tris(pentafluorophenyl)corrole trianion; TBP8Cz = 2,3,7,8,12,13,17,18-octa(4-tert-butylphenyl)corrolazine). X-ray quality crystals of each of the Mn(III) haloamide complexes were obtained by cooling concentrated acetonitrile solutions to -35 °C; solid-state structures of 13 are collected in Figure and relevant refinement data are collected in Tables and N-iodoamide complexes of a transition metal, respectively. For comparison of the metrical parameters of 13 with known chloroamides, see Table . The wavelength dependence of the observed photochemistry of 13e was evaluated using 335 nm, 400 nm, and 495 nm long-pass filters. Only the 335 nm filter resulted in the spectral evolution illustrated in Figure ; no photoconversion was observed with a 400 or 495 nm long pass filter during the time scale of the experiment. However, prolonged photolysis (5 days) of 13e with a 400 nm long pass filter yielded aminated THF ( ) (40%, Table ). These data are consistent with photochemistry arising from excitation of the LMCT band at 386 nm. Similar observations were reported by Suslick, that excitation of the analogous LMCT in Mn nitrate complexes was critical to accessing the corresponding Mn oxo complexes. Complex 13e participates in nitrene transfer photochemistry with a variety of substrates that are commonly encountered in Mn-catalyzed nitrene transfer chemistry (Figure ). Photolysis of 13e (λ > 335 nm) in a 4:1 MeCN:2-Me-THF solution results in sulfonamide 16 (19% yield), the product of formal nitrene insertion into the less hindered α-C-H bond. To probe the C-H bond strength requirement for amination, we examined the photochemical amination of toluene (C-H bond dissociation energy (BDE) = 89.7 kcal/mol ) and cyclohexane (C-H BDE = 99.5 kcal/mol ): Toluene underwent benzylic amination to afford compound 17 in 40% yield; cyclohexane did not participate in detectable amination chemistry. Photolysis of 13e in the presence of styrene results in aziridine 18 in 30% yield. In all cases, the mass balance is accounted for by TsNH2 and transfer of the NTs fragment requires photochemical activation: Thermolysis of 13e in the presence of these substrates results in 15 and TsNH2.