Over or under: hydride attack at the metal versus the coordinated nitrosyl ligand in ferric nitrosyl porphyrins.
نویسندگان
چکیده
Hydride attack at a ferric heme-NO to give an Fe-HNO intermediate is a key step in the global N-cycle. We demonstrate differential reactivity when six- and five-coordinate ferric heme-NO models react with hydride. Although Fe-HNO formation is thermodynamically favored from this reaction, Fe-H formation is kinetically favored for the 5C case.
منابع مشابه
Fast nitroxyl trapping by ferric porphyrins.
Iron(II) porphyrin nitrosyl complexes are obtained in high yields from the reaction of iron(III) porphyrins with the nitroxyl donors sodium trioxodinitrate and toluensulfohydroxamic acid. The reaction was found to proceed both in organic solvents and in aqueous media from iron(III) (meso-tetraphenyl) porphyrinate ([FeIII(TPP)]+) and iron(III) meso-tetrakis (4-sulfonatophenyl) porphyrinate ([FeI...
متن کاملElectronic and stereochemical characterizations of the photoinduced intermediates of nitrosyl complexes of metal (S = 5/2)-substituted hemoproteins trapped at low temperature.
Low temperature photolysis of nitric oxide from the nitrosyl complexes of ferric myoglobin (NO-Fe(III)Mb) and manganese(II)-porphyrin-substituted myoglobin (NO-Mn(II)Mb) was examined by electron paramagnetic resonance (EPR) spectroscopy in order to elucidate the electronic and structural natures of the photoinduced intermediates of these hemoprotein-ligand complexes trapped at low temperature. ...
متن کاملElectrochemistry and spectroelectrochemistry of iron porphyrins in the presence of nitrite
The reaction of nitrite with ferric and ferrous porphyrins was examined using visible, infrared and NMR spectroscopy. Solutions of either ferric or ferrous porphyrin were stable in the presence of nitrite, with only complexation reactions being observed. Under voltammetric conditions, though, a rapid reaction between nitrite and iron porphyrins was observed to form the nitrosyl complex, Fe(P)(N...
متن کاملIron Nitrosyl “Natural” Porphyrinates: Does the Porphyrin Matter?
The synthesis and spectroscopic characterization of three five-coordinate nitrosyliron(II) complexes, [Fe(Porph)(NO)], are reported. These three nitrosyl derivatives, where Porph represents protoporphyrin IX dimethyl ester, mesoporphyrin IX dimethyl ester, or deuteroporphyrin IX dimethyl ester, display notable differences in their properties relative to the symmetrical synthetic porphyrins such...
متن کاملSUPPORTED CYCLOPENTADIENYLMETAL CARBONYL COMPLEXES II *. POLYSTYRENE.sUPPORTED CARBONYL AND NITROSYL DERIVATIVES OF GROUP VI TRANSITION METALS
Tricarbonyl hydride derivatives of cyclopentadienyl-chromium, -molybdenum and -tungsten compounds covalently linked to a macroreticular polystyrene support are obtained by treatment of polystyrene-attached cyclopentadienyl anions with the respective metal hexacarbonyl and subsequent acidification. In contrast to the ease with which unsupported cyclopentaruenyl·chromium and -molybdenum tricarbon...
متن کاملذخیره در منابع من
با ذخیره ی این منبع در منابع من، دسترسی به آن را برای استفاده های بعدی آسان تر کنید
برای دانلود متن کامل این مقاله و بیش از 32 میلیون مقاله دیگر ابتدا ثبت نام کنید
ثبت ناماگر عضو سایت هستید لطفا وارد حساب کاربری خود شوید
ورودعنوان ژورنال:
- Dalton transactions
دوره 45 45 شماره
صفحات -
تاریخ انتشار 2016