naa a22 4500 510734537 CHVBK 20180411083005.0 cr unu---uuuuu 180411e20130701xx s 000 0 eng 10.1007/s12039-013-0447-1 doi (NATIONALLICENCE)springer-10.1007/s12039-013-0447-1 NO2-induced synthesis of nitrato-iron(III) porphyrin with diverse coordination mode and the formation of isoporphyrin‡ [Elektronische Daten] [JAGANNATH BHUYAN, SABYASACHI SARKAR] Two nitrato-iron(III) porphyrinates [Fe(4-Me-TPP)(NO3)] 1 and [Fe(4-OMe-TPP)(NO3)] 2 are reported. Interestingly, [Fe(4-Me-TPP)(NO3)] 1 has nitrate ion coordinated as monodentate (by single oxygen atom), while [Fe(4-OMe-TPP)(NO3)] 2 has nitrate coordination through bidentate mode. Compound 1 was found serendipitously in the reaction of [Fe(4-Me-TPP)Cl] with nitrous acid, which was performed for the synthesis of nitro-iron(III) porphyrin, [Fe(4-Me-TPP)NO2]. The compound 2 was synthesized by passing NO2 gas through a solution of [Fe(4-OMe-TPP)]2O. Upon passing NO2 gas through a solution of a μ-oxo-dimer, [Fe(4-Me-TPP)]2O also produces 1. It is interesting that in more electron-rich porphyrin 2, binding of the nitrate in a symmetrical bidentate way while in less electron-rich porphyrin 1, binding of the anion is unidentate by a terminal oxygen atom. However, it is expected that the energy difference between the monodentate and bidentate coordination mode is very small and the interchange between these coordination is possible. Upon passing NO2 gas through a solution of $\upmu $ -oxo-dimeric iron(III) porphyrin, the nitrato-iron(III) porphyrin forms first, that later gets oxidized to π-cation radical to yield hydroxy-isoporphyrin in the presence of trace amount of water. These nitrato-iron(III) porphyrinates in moist air slowly converted back to their respective $\upmu $ -oxo-dimeric iron(III) porphyrins. Graphical Abstract [Fe(4-Me-TPP)]2O and [Fe(4-OMe-TPP)]2O react with NO2 to produce nitratoiron( III) porphyrin with monodentate and bidenate nitrate coordination, respectively. Further passage of NO2 oxidized these to π-cation radical to yield hydroxy-isoporphyrin in the presence of moisture. But nitrato-iron(III) porphyrinates in moist air slowly converted back to their respective μ-oxodimeric iron(III) porphyrins. Indian Academy of Sciences, 2013 Porphyrin nationallicence nitrate nationallicence iron nationallicence nitric oxide nationallicence X-ray crystallography nationallicence BHUYAN JAGANNATH Department of Chemistry, Indian Institute of Technology Kanpur, 208 016, Kanpur, India aut SARKAR SABYASACHI Department of Chemistry, Bengal Engineering and Science University, Shibpur, 711 103, Howrah, India aut Journal of Chemical Sciences Springer India 125/4(2013-07-01), 707-714 0974-3626 125:4<707 2013 125 12039 https://doi.org/10.1007/s12039-013-0447-1 text/html Onlinezugriff via DOI 1 research-article jats NATIONALLICENCE 856 40 https://doi.org/10.1007/s12039-013-0447-1 text/html Onlinezugriff via DOI NATIONALLICENCE 700 1- BHUYAN JAGANNATH Department of Chemistry, Indian Institute of Technology Kanpur, 208 016, Kanpur, India aut NATIONALLICENCE 700 1- SARKAR SABYASACHI Department of Chemistry, Bengal Engineering and Science University, Shibpur, 711 103, Howrah, India aut NATIONALLICENCE 773 0- Journal of Chemical Sciences Springer India 125/4(2013-07-01), 707-714 0974-3626 125:4<707 2013 125 12039 Metadata rights reserved Springer special CC-BY-NC licence nationallicence BK010053 XK010053 XK010000 NATIONALLICENCE NATIONALLICENCE NL-springer