30379-87-4Relevant articles and documents
The reaction of [Fe(pic)3] with hydrogen peroxide: A UV-visible and EPR spectroscopic study (Hpic = picolinic acid)
Jain, Sneh L.,Bhattacharyya, Pravat
, p. 2696 - 2701 (2007/10/03)
The Gif family of catalysts, based on an iron salt and O2 or H2O2 in pyridine, allows the oxygenation of cyclic saturated hydrocarbons to ketones and alcohols under mild conditions. The reaction between [Fe(pic)3] and hydrogen peroxide in pyridine under GoAggIII (Fe(III)/Hpic catalyst) conditions was investigated by UV-visible spectrophotometry. Reactions were monitored at 430 and 520 nm over periods ranging from a few minutes to several hours at 20 °C. A number of kinetically stable intermediates were detected, and their relevance to the processes involved in the assembly of the active GoAggIII catalyst was determined by measuring the kinetics in the presence and absence of cyclohexane. EPR measurements at 110 K using hydrogen peroxide and t-BuOOH as oxidants were used to further probe these intermediates. Our results indicate that in wet pyridine [Fe(pic)3] undergoes reversible dissociation of one picolinate ligand, establishing an equilibrium with [Fe(pic) 2(py)(OH)]. Addition of aqueous hydrogen peroxide rapidly generates the high-spin complex [Fe(pic)2(py)(η1-OOH)] from the labilised hydroxy species. Subsequently the hydroperoxy species undergoes homolysis of the Fe-O bond, generating HOO. and [Fe(pic) 2(py)2], the active oxygenation catalyst. The Royal Society of Chemistry 2005.
Iron-induced activation of hydrogen peroxide for the direct ketonization of methylenic carbon [c-C6H12 → c-C6H10(O)] and the dioxygenation of acetylenes and arylolefins
Sheu, Ceshing,Richert, Silvia A.,Cofré, Pablo,Ross Jr., Blango,Sobkowiak, Andrzej,Sawyer, Donald T.,Kanofsky, Jeffrey R.
, p. 1936 - 1942 (2007/10/02)
In pyridine/acetic acid solvent bis(picolinato)iron(II) [Fe(PA)2], (2,6-dicarboxylatopyridine)iron(II) [Fe(DPA)], and their μ-oxo dimers [(PA)2FeOFe(PA)2 and (DPA)FeOFe(DPA)] catalyze hydrogen peroxide for the selective ketonization of methylenic carbons (>CH2 → C=O) and the dioxygenation of acetylenes to α-diketones and arylolefins to aldehydes. Cyclohexane is transformed with 72% efficiency (c-C6H12 oxidized per two HOOH) to give 95% cyclohexanone and 5% cyclohexanol, ethyl benzene with 51% efficiency to give acetophenone as the only detectable product, and n-hexane with 52% efficiency to give 53% 3-hexanone, 46% 2-hexanone, and 2(s) or (Me4N)O2(s) in a pyridine/acetic acid solvent system are catalyzed by several iron complexes [(py)4FeCl2, (py)4Fe(OAc)2, FeCl3·6H2O, (MeCN)4Fe(ClO4)2, (Ph3PO)4Fe(ClO4)2, Fe(PA)2, and (PA)2FeOFe(PA)2] to give HOOH and transform methylenic carbons to ketones, and to dioxygenate acetylenes and arylolefins. Electrolytic reduction of dioxygen (O2) in the same solvent/catalyst systems results in analogous substrate transformations. The Fe(PA)2 complex is uniquely efficient and exhibits catalytic turnover for KO2(s) suspensions as well as for electro-reduced O2. All systems appear to produce a common reactive intermediate 3 [(PA)2FeOOOFe(PA)2] via in situ formation of HOOH and (PA)2FeOFe(PA)2 (1).
Ligand-centered redox processes for MnL3, FeL3, and CoL3 complexes (L = acetylacetonate, 8-quinolinate, picolinate, 2,2′-bipyridyl, 1,10-phenanthroline) and for their tetrakis(2,6-dichlorophenyl)porphinato complexes [M(Por)]
Richert, Silvia A.,Tsang, Paul K. S.,Sawyer, Donald T.
, p. 2471 - 2475 (2008/10/08)
The potentials for the ML3-/ML3 couple of MnL3, FeL3, and CoL3 complexes (L = acetylacetonate, 8-quinolinate, picolinate, 2,2′-bipyridyl, 1,10-phenanthroline) occur at substantially less positive values than those for their zinc analogues and are clearly ligand-centered. The negative shift in potential for these ligand oxidations is proportional to their metal-ligand covalent-bond energies. The reductions for the bipyridyl and phenanthroline complexes of these transition metals also are ligand-centered. Electrochemical characterization of tetrakis(2,6-dichlorophenyl)porphine and of its neutral porphinato complexes with Zn, Mn, Fe, and Co indicates that electron transfer occurs within the porphyrin ring and that the metal-porphyrin bonding involves covalent σ bonds between dnsp valence electrons of the neutral metal (or hydrogen atoms of porphine) and two pyrrole p electrons of the uncharged porphyrin.