Abstract
Reduction of previously reported iminyl radical ((Ar)L)FeCl((•)N(C(6)H(4)-p-(t)Bu)) (2) with potassium graphite furnished the corresponding high-spin (S = (5)/(2)) imido ((Ar)L)Fe(N(C(6)H(4)-p-(t)Bu)) (3) ((Ar)L = 5-mesityl-1,9-(2,4,6-Ph(3)C(6)H(2))dipyrrin). Oxidation of the three-coordinate imido ((Ar)L)Fe(NAd) (5) with chlorotriphenylmethane afforded ((Ar)L)FeCl((•)NAd) (6) with concomitant expulsion of Ph(3)C(C(6)H(5))CPh(2). The respective aryl/alkyl imido/iminyl pairs (3, 2; 5, 6) have been characterized by EPR, zero-field (57)Fe Mössbauer, magnetometry, single crystal X-ray diffraction, XAS, and EXAFS for 6. The high-spin (S = (5)/(2)) imidos exhibit characteristically short Fe-N bonds (3: 1.708(4) Å; 5: 1.674(11) Å), whereas the corresponding iminyls exhibit elongated Fe-N bonds (2: 1.768(2) Å; 6: 1.761(6) Å). Comparison of the pre-edge absorption feature (1s → 3d) in the X-ray absorption spectra reveals that the four imido/iminyl complexes share a common iron oxidation level consistent with a ferric formulation (3: 7111.5 eV, 2: 7111.5 eV; 5: 7112.2 eV, 6: 7112.4 eV) as compared with a ferrous amine adduct ((Ar)L)FeCl(NH(2)Ad) (7: 7110.3 eV). N K-edge X-ray absorption spectra reveal a common low-energy absorption present only for the iminyl species 2 (394.5 eV) and 6 (394.8 eV) that was assigned as a N 1s promotion into a N-localized, singly occupied iminyl orbital. Kinetic analysis of the reaction between the respective iron imido and iminyl complexes with toluene yielded the following activation parameters: E(a) (kcal/mol) 3: 12.1, 2: 9.2; 5: 11.5, 6: 7.1. The attenuation of the Fe-N bond interaction on oxidation from an imido to an iminyl complex leads to a reduced enthalpic barrier [Δ(ΔH(‡)) ≈ 5 kcal/mol]; the alkyl iminyl 6 has a reduced enthalpic barrier (1.84 kcal/mol) as compared with the aryl iminyl 2 (3.84 kcal/mol), consistent with iminyl radical delocalization into the aryl substituent in 2 as compared with 6.