Catalytic C-H oxidations by nonheme mononuclear Fe(II) complexes of two pentadentate ligands: Evidence for an Fe(IV) oxo intermediate

Mitra, Mainak; Nimir, Hassan; Hrovat, David A.; Shteinman, A. A.; Richmond, Michael G.; Costas, Miguel; Nordlander, Ebbe

doi:10.1016/j.molcata.2016.10.010

Cited by 28 publications

(8 citation statements)

References 52 publications

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“…The results could be further improved by performing the reactions in the presence of acetic acid (AcOH). [51,52] In line with the results obtained in the absence of acetic acid, complexes 7 and 8 (entries 14 and 17, Table 1) were the most efficient catalysts exhibiting combined yields of alcohol and ketone products of 32% for iron and 40% for manganese, in all cases resulting from methylene oxidation. Moreover, iron and manganese complexes bearing the deuterated mcp ligand (3 and 4) were also tested.…”

Section: Reaction Development Employing 2233-tetramethylbutane As Mod...supporting

confidence: 78%

Catalytic Oxidation of Primary C–H Bonds in Alkanes with Bioinspired Catalysts

Dantignana

Costas

2020

Chimia

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Catalytic oxidation of primary C–H bonds of alkanes with a series of iron and manganese catalysts is investigated. Products resulting from oxidation of methylenic sites are observed when hexane (S1) is used as model substrate, while corresponding primary C–H bonds remain unreactive. However, by using 2,2,3,3-tetramethylbutane (S2) as model substrate, which only contains primary alkyl C–H bonds, oxidation takes place catalytically using a combination of hydrogen peroxide, a manganese catalyst and acetic acid as co-catalyst, albeit with modest yields (up to 4.4 TON). Complexes bearing tetradentate aminopyridine ligands provide the best yields, while a related pentadentate ligand provides smaller product yields. The chemoselectivity of the reaction is solvent dependent. Carboxylic acid 2b is observed as major product when the reaction takes place in acetonitrile, because of the facile overoxidation of the first formed alcohol product 2a. Instead the corresponding primary alcohol 2a becomes dominant in reactions performed in 2,2,2-trifluoroethanol (TFE). Polarity reversal of the hydroxyl moiety arising from the strong hydrogen bond donor ability of the latter solvent accounts for the unusual product chemoselectivity of the reaction. The significance of the current results in the context of light alkane oxidation is discussed.

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Section: Reaction Development Employing 2233-tetramethylbutane As Mod...supporting

confidence: 78%

Catalytic Oxidation of Primary C–H Bonds in Alkanes with Bioinspired Catalysts

Dantignana

Costas

2020

Chimia

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“…The complex [Fe( 3 )(CH 3 CN)](ClO 4 ) 2 was shown by Nordlander to be also catalytic active in the oxidation of cyclohexane, where 3 is a pentadentate ligand bearing benzimidazole and pyridyl units (Table , entry 4) . Employing H 2 O 2 , the alcohol/ketone ratio is low and points toward a radical mechanism.…”

Section: Oxygenations Of Hydrocarbonsmentioning

confidence: 99%

Recent Advances in Iron Catalyzed Oxidation Reactions of Organic Compounds

Bauer

2017

Israel Journal of Chemistry

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Iron-catalyzed oxidation reactions have been increasingly investigated in the past two decades and have seen a major increase in research activity. This review article demonstrates the vigorous research activities in the field based on examples from the most recent literature. Catalyst systems are discussed that are active in the oxygenation of alkanes and alkenes to obtain alcohols, ketones or epoxides. Iron-catalyzed oxidation of alcohols to the corresponding carbonyl units are also included. Enantioselective and heterogeneous catalyst systems are presented as well, and a brief overview of mechanistic pictures is given. B. Bauer was born in Nuremberg, Germany. He received PhD degree in 2003 from the University of Erlangen-Nuremberg; under the supervision of Prof. John A. Gladysz, he performed ring closing metathesis reactions in the coordination sphere of transition metals to obtain macrocyclic metal complexes. He performed postdoctoral research at the University of California, Riverside with Keith Hollis, working on rhodium and iridium carbene complexes with catalytic activity in hydroamination and hydrosilylation reactions. In 2005 he joined Illinois Wesleyan University for one year as a Visiting Assistant Professor. In 2006 he joined the University of Missouri -St. Louis as an Assistant Professor, and became promoted to Associate Professor in 2012. His research interests are the synthesis and characterization of ruthenium and iron complexes to be employed in catalytic processes. His work on ruthenium mainly concerns the catalytic activation of propargylic alcohols and their derivatives toward nucleophilic substitution reactions. In the area of iron catalysis, he published a number of iron complexes to be catalytically active in the oxidation of hydrocarbons and alcohols.

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“…Complex 6 does not exhibit catalytic activity in the oxidation of alkanes with TBHP, which can be associated with its relatively rapid decomposition or transformation into a catalytically inactive species under the reaction conditions. It should be noted that the oxidation of alcohols with TBHP is effectively catalyzed by both As mentioned above, mononuclear iron derivatives are often less active in alkane oxidation reactions, which proceed according to Fenton-like mechanism involving hydroxyl radicals [41][42][43][44][45][46][47][48][49][50][51][52][53][54][55][56][57][58][59].…”

Section: Oxidation Catalyzed By Copper Complexesmentioning

confidence: 99%

Oxidation of Organic Compounds with Peroxides Catalyzed by Polynuclear Metal Compounds

Shul’pin

Shul’pina

2021

Catalysts

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The review describes articles that provide data on the synthesis and study of the properties of catalysts for the oxidation of alkanes, olefins, and alcohols. These catalysts are polynuclear complexes of iron, copper, osmium, nickel, manganese, cobalt, vanadium. Such complexes for example are: [Fe2(HPTB)(m-OH)(NO3)2](NO3)2·CH3OH·2H2O, where HPTB-¼N,N,N0,N0-tetrakis(2-benzimidazolylmethyl)-2-hydroxo-1,3-diaminopropane; complex [(PhSiO1,5)6]2[CuO]4[NaO0.5]4[dppmO2]2, where dppm-1,1-bis(diphenylphosphino)methane; (2,3-η-1,4-diphenylbut-2-en-1,4-dione)undecacarbonyl triangulotriosmium; phenylsilsesquioxane [(PhSiO1.5)10(CoO)5(NaOH)]; bi- and tri-nuclear oxidovanadium(V) complexes [{VO(OEt)(EtOH)}2(L2)] and [{VO(OMe)(H2O)}3(L3)]·2H2O (L2 = bis(2-hydroxybenzylidene)terephthalohydrazide and L3 = tris(2-hydroxybenzylidene)benzene-1,3,5-tricarbohydrazide); [Mn2L2O3][PF6]2 (L = 1,4,7-trimethyl-1,4,7-triazacyclononane). For comparison, articles are introduced describing catalysts for the oxidation of alkanes and alcohols with peroxides, which are simple metal salts or mononuclear metal complexes. In many cases, polynuclear complexes exhibit higher activity compared to mononuclear complexes and exhibit increased regioselectivity, for example, in the oxidation of linear alkanes. The review contains a description of some of the mechanisms of catalytic reactions. Additionally presented are articles comparing the rates of oxidation of solvents and substrates under oxidizing conditions for various catalyst structures, which allows researchers to conclude about the nature of the oxidizing species. This review is focused on recent works, as well as review articles and own original studies of the authors.

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Catalytic C-H oxidations by nonheme mononuclear Fe(II) complexes of two pentadentate ligands: Evidence for an Fe(IV) oxo intermediate

Cited by 28 publications

References 52 publications

Catalytic Oxidation of Primary C–H Bonds in Alkanes with Bioinspired Catalysts

Catalytic Oxidation of Primary C–H Bonds in Alkanes with Bioinspired Catalysts

Recent Advances in Iron Catalyzed Oxidation Reactions of Organic Compounds

Oxidation of Organic Compounds with Peroxides Catalyzed by Polynuclear Metal Compounds

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