ABSTRACT
Herein, we show that the reaction of a mononuclear FeIII(OH) complex (1) with N-tosyliminobenzyliodinane (PhINTs) resulted in the formation of a FeIV(OH) species (3). The obtained complex 3 was characterized by an array of spectroscopic techniques and represented a rare example of a synthetic FeIV(OH) complex. The reaction of 1 with the one-electron oxidizing agent was reported to form a ligand-oxidized FeIII(OH) complex (2). 3 revealed a one-electron reduction potential of -0.22 V vs Fc+/Fc at -15 °C, which was 150 mV anodically shifted than 2 (Ered = -0.37 V vs Fc+/Fc at -15 °C), inferring 3 to be more oxidizing than 2. 3 reacted spontaneously with (4-OMe-C6H4)3C⢠to form (4-OMe-C6H4)3C(OH) through rebound of the OH group and displayed significantly faster reactivity than 2. Further, activation of the hydrocarbon C-H and the phenolic O-H bond by 2 and 3 was compared and showed that 3 is a stronger oxidant than 2. A detailed kinetic study established the occurrence of a concerted proton-electron transfer/hydrogen atom transfer reaction of 3. Studying one-electron reduction of 2 and 3 using decamethylferrocene (Fc*) revealed a higher ket of 3 than 2. The study established that the primary coordination sphere around Fe and the redox state of the metal center is very crucial in controlling the reactivity of high-valent Fe-OH complexes. Further, a FeIII(OMe) complex (4) was synthesized and thoroughly characterized, including X-ray structure determination. The reaction of 4 with PhINTs resulted in the formation of a FeIV(OMe) species (5), revealing the presence of two FeIV species with isomer shifts of -0.11 mm/s and = 0.17 mm/s in the Mössbauer spectrum and showed FeIV/FeIII potential at -0.36 V vs Fc+/Fc couple in acetonitrile at -15 °C. The reactivity studies of 5 were investigated and compared with the FeIV(OH) complex (3).
ABSTRACT
We report the role of chemically expanded graphite in the fabrication of high-performance graphene oxide fibers by wet spinning. X-ray diffraction peak showed that the interplanar distance of the expanded graphene oxide (EGO) fiber was more than that of graphene oxide (GO) fiber due to the expanded graphite. X-ray photon spectroscopy analysis revealed that EGO was more oxidized than GO. The hydrogen bonding network and secondary intermolecular interaction made the EGO aqueous solution more stable and crystalline, and it was able to be stretched in the coagulation bath. Morphological analysis showed the excellent alignment and compactness of EGO sheets in the fibers. The increased interplanar distance between the EGO sheets favored the edge-to-edge interaction more than the basal plane interaction within the fiber, thus resulting in high mechanical strength (492 MPa) and increased elongation (6.1%).
