Cyclopentadienyliron complexes of nitrosobenzene: Preparation, structure and reactivity with olefins

Stephens, Jeremy C.; Khan, Masood A.; Nicholas, Kenneth M.

doi:10.1016/j.jorganchem.2005.06.045

Cited by 15 publications

(12 citation statements)

References 32 publications

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“…When the catalyst contain the pentamethylcyclopentadienyl ligand instead of the unsubstituted Cp, it had been earlier found that deactivation can occur by the formation of a complex in which a methyl group of the ligand has been aminated . On the other hand, the nitrosobenzene complex [CpFe(CO) 2 (κ 1 ‐N‐PhNO)][BF 4 ], prepared by reaction of [CpFe(CO) 2 I] with nitrosobenzene and AgBF 4 , was found to afford only trace amounts of allylic amine and is not an active intermediate in the catalytic cycle …”

Section: Synthesis Of N‐heterocycles By Inter‐molecular Cyclization Rmentioning

confidence: 99%

“…[143] On the other hand, the nitrosobenzene complex [CpFe(CO) 2 (k 1 -N-PhNO)][BF 4 ], prepared by reaction of [CpFe(CO) 2 I] with nitrosobenzene and AgBF 4 , was found to afford only trace amounts of allylic amine and is not an active intermediate in the catalytic cycle. [145] The application of the [Cp*Fe(CO) 2 ] 2 -catalyzed photostimulated reaction was also extended to some cyclic olefins (cyclopentene, cyclohexene, cyclooctene). [146] By comparison with the results previously obtained by using the same catalyst, it appears that the reaction of internal olefin is most of the times slower than that of terminal ones, although the selectivity in allylic amine is equally good.…”

Section: Synthesis Of Allylic Amines From Nitroarenes and Unfunctionamentioning

confidence: 99%

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Transition Metal Catalyzed Reductive Cyclization Reactions of Nitroarenes and Nitroalkenes

2019

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Nitroarenes are the entry point for the production of most nitrogen‐containing aromatic compounds. Thus, any transformation that leads directly from them to the final product allows saving one or more synthetic steps. This review deals with homogeneously catalyzed reactions leading to the formation of N‐heterocyclic compounds from nitroarenes or nitroalkenes in one pot. Reactions that lead to the intermediate formation of amines are not considered. Carbon monoxide is the most often employed reductant because it allows selective reactions, is cheap, and only produces CO2 as stoichiometric byproduct. However, the difficulty in handling pressurized CO has stimulated in recent years the development of CO‐surrogates, that is molecules able to liberate CO during the reaction. The use of phosphines and diols has also been developed in conjunction with molybdenum catalysts. The review focusses in more detail on the literature in the period 2006–2018, but reference to earlier work is made when necessary to put recent results in a more general context.

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Section: Synthesis Of N‐heterocycles By Inter‐molecular Cyclization Rmentioning

confidence: 99%

Section: Synthesis Of Allylic Amines From Nitroarenes and Unfunctionamentioning

confidence: 99%

Transition Metal Catalyzed Reductive Cyclization Reactions of Nitroarenes and Nitroalkenes

2019

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“…The N–O bond length of 1.321(4) Å in 2a is significantly longer than that found for uncoordinated PhNO (1.240(7) Å) . In addition, this N–O bond distance is intermediate between the typical ranges observed for neutral PhNO 0 (1.257–1.32 Å) − and anionic radical PhNO •– (1.322–1.35 Å), , but shorter than anionic PhNO 2– ligands (1.37–1.49 Å) , with the same μ−η 1 :η 1 coordination mode. Notably, the phenyl ring of the bridging PhNO ligand is nearly perpendicular to the plane through C27, N1, and O1 atoms with a dihedral angle of 84.5(4)°.…”

Section: Resultsmentioning

confidence: 64%

Generation of a Sulfinamide Species from Facile N–O Bond Cleavage of Nitrosobenzene by a Thiolate-Bridged Diiron Complex

Yang

Wang

et al. 2021

J. Am. Chem. Soc.

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The activation of nitrosobenzene promoted by transition-metal complexes has gained considerable interest due to its significance for understanding biological processes and catalytic C–N bond formation processes. Despite intensive studies in the past decades, there are only limited cases where electron-rich metal centers were commonly employed to achieve the N–O or C–N bond cleavage of the coordinated nitrosobenzene. In this regard, it is significant and challenging to construct a suitable functional system for examining its unique reactivity toward reductive activation of nitrosoarene. Herein, we present a {Fe2S2} functional platform that can activate nitrosobenzene via an unprecedented iron-directed thiolate insertion into the N–O bond to selectively generate a well-defined diiron benzenesulfinamide complex. Furthermore, computational studies support a proposal that in this concerted four-electron reduction process of nitrosobenzene the iron center serves as an important electron shuttle. Notably, compared to the intact bridging nitrosoarene ligand, the benzenesulfinamide moiety has priority to convert into aniline in the presence of separate or combined protons and reductants, which may imply the formation of the sulfinamide species accelerates reduction process of nitrosoarene. The reaction pattern presented here represents a novel activation mode of nitrosobenzene realized by a thiolate-bridged diiron complex.

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“…N-O distances of [3d,m,o,s] + (1.251(3)-1.272(12) Å), featuring more electron-donating dppe ancillary ligands, are slightly elongated relative to the carbonyl complex [Fe{N(O)-Ph}(CO)2Cp] + (1.226(3) Å),18 indicating greater Fe-N(O) back bonding. The Fe-O=NR binding mode was not observed in any of the compounds studied here 8.…”

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confidence: 99%

Rip It off: Nitro to Nitroso Reduction by Iron Half-Sandwich Complexes

et al. 2021

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Activation of [FeCl(dppe)Cp] (1) by chloride abstraction with Na[BAr X 4] (X = F: [B(3,5-(CF3)2-C6H3)4]; X = Cl: [B(3,5-Cl2-C6H3)4]) permits reaction with a range of nitro aromatics, RC6H4NO2 (R = halogen, Me, OMe, NO2 or NMe2) to give cationic iron nitroso complexes [Fe{N(O)-C6H4R}(dppe)Cp] + ([3] + ). Similar reactions of 1 and NaHowever, reactions of 1 and Na [BAr X 4] with 4-nitrophenol gave the first example of a bench-stable iron half-sandwich phenolate complex [Fe(OC6H4NO2)(dppe)Cp] + rather than NO2 activation. The formation of complexes [3] + likely proceeds via the unusual, bluecoloured bimetallic species [{Fe(dppe)Cp}2{,κ 2 O,O'-O2NAr}] 2+ . This compound undergoes N-O bond cleavage resulting in [3] + and a Fe IV =O species, which reacts via an internal C-H activation of the dppe ligand to give [Fe III (κ 3 O,P,P'-P(2-O-C6H4)(Ph)-C2H4-PPh2)Cp] + . Complexes [3] + are stable under ambient conditions, readily purified by column chromatography and isolated in up to 50 % yield, considering 0.5 equiv of 1 to be required as the oxygen acceptor.

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Cyclopentadienyliron complexes of nitrosobenzene: Preparation, structure and reactivity with olefins

Cited by 15 publications

References 32 publications

Transition Metal Catalyzed Reductive Cyclization Reactions of Nitroarenes and Nitroalkenes

Transition Metal Catalyzed Reductive Cyclization Reactions of Nitroarenes and Nitroalkenes

Generation of a Sulfinamide Species from Facile N–O Bond Cleavage of Nitrosobenzene by a Thiolate-Bridged Diiron Complex

Rip It off: Nitro to Nitroso Reduction by Iron Half-Sandwich Complexes

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