A kinetic study of the mechanisms of S NAr reactions of neutral and cationic metal-complexed halogenoarenes with methoxide ion

Knipe, A. C.; McGuinness, Samuel J.; Watts, William E.

doi:10.1039/p29810000193

Cited by 23 publications

(8 citation statements)

References 1 publication

(1 reference statement)

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“…The advantage of using the CpFe' moiety is primarily due to the activating ability of this group towards displacement reactions. This was demonstrated clearly by the kinetic study carried out by Knipe et al (20,21). As well, the low toxicity and cost of this type of FeCp' complexation makes this route attractive in the synthesis of substituted aroof the cpFe+ complexes of chloroarenes in the synthesis of potentially biologically active molecules (2)(3)(4)(5).…”

Section: Introduction Matic Compounds Our Research Interest Is Focusmentioning

confidence: 66%

Ironcyclopentadienyl mediated 2-alkyl-2-arylphenylsulphonylacetonitrile synthesis

Abd‐El‐Aziz¹,

Denus²,

Hutton³

1995

Can. J. Chem.

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Abstract:A unique route to the synthesis of 2-alkyl-2-arylphenylsulphonylacetonitriles via the nucleophilic aromatic substitution (SNAr) of chloroarene cyclopentadienyliron complexes with 2-alkyl phenylsulphonylacetonitriles has been investigated. Reactions of chloroarene complexes (la-6) with 2-alkyl phenylsulphonylacetonitrile (2a,b) in the presence of K,CO, in DMF at room temperature led to the formation of complexes 3a-d and 4a,c,d in good yields. The use of alkylated phenylsulphonylacetonitriles as nucleophiles in the reactions with thep-dichlorobenzene complex ( l e ) allowed the formation of the disubstituted complexes (5,6). Photolytic demetallation provided an efficient route to the liberation of the arylated phenylsulphonylacetonitriles 7a-d, 8a,c,d, 9, and 10.Key words: chloroarene, phenylsulphonylacetonitrile, nucleophilic substitution.RCsumC : On explore une mtthode originale de synthbse des 2-alkyl-2-arylphCnylsulphonylacCtonitriles via la substitution aromatique nuclCophile (SNAr) des complexes du chloroarbnecyclopentadiCnyl de fer avec les 2-alkylphCnylsulphonylacCtonitriles. Les rkactions des complexes de choroarbnes (10-6) avec le 2-alkylphCnylsulphonylacCtonitrile (2a,b) en presence de K,CO, dans le DMF a la temperature ambiante conduisent, avec de bons rendements, ? i la formation des complexes 3a-d et 4a,c,d. L'emploi des phCnylsulphonylacCtonitriles alkyICs comme nuclCophiles dans la reaction avec le complexe de p-dichlorobenzbne ( l e ) permet la formation de complexes disubstituCs ( 5 , 6 ) . La dCmCtallation photolytique foumit une excellente voie d'acces a la liberation des phCnylsulphonylacCtonitriles 7a-d, 8a,c,d, 9 et 10.

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Section: Introduction Matic Compounds Our Research Interest Is Focusmentioning

confidence: 66%

Ironcyclopentadienyl mediated 2-alkyl-2-arylphenylsulphonylacetonitrile synthesis

Abd‐El‐Aziz¹,

Denus²,

Hutton³

1995

Can. J. Chem.

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“…Treatment of 4 and 10 with PPh 3 gave 17 and 18 , respectively (Scheme ). Due to the high electrophilicities of (arene)Mn(CO) 3 + , PPh 3 selectively attacks the manganese carbonyls. When the PPh 3 -substituted chromium compounds [(η 6 -9,10-dihydroanthracene)Cr(CO) 2 PPh 3 ] ( 19 ) and [(η 6 - trans -stilbene)Cr(CO) 2 PPh 3 ] ( 20 ) were reacted with (naphthalene)Mn(CO) 3 + , we only recovered the reactants.…”

Section: Resultsmentioning

confidence: 99%

Preparation of Chromium−Manganese Diarene Heterobimetallic Complexes Using a Mn(CO)₃⁺ Transfer Reaction

Lee

et al. 1996

Organometallics

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The reaction of mono-Cr(CO)3 complexes of a number of aromatic compounds containing two arene groups with the Mn(CO)3 + transfer agent [(naphthaleneMn(CO)3]+ gave new Cr/Mn diarene heterobimetallic compounds, e.g., (OC)3Cr(η6-C6H5CHCHC6H5-η6)Mn(CO)3 +. This and two others of these compounds were characterized by X-ray diffraction. The two metal carbonyl groups were found to be on the same face of the aromatic hydrocarbon molecules in a syn arrangement.

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“…Prior studies of aromatic nucleophilic substitution ("S N Ar") reactions of halogen-modified aromatics have typically observed that the different halogens yield a reactivity trend that is the opposite of that we observe. 59 Elucidation of a detailed mechanism for the surface reaction is complicated by the presence of multiple crystal faces and the many overlapping features due to surface −OH groups and modes of adsorbed water. Prior studies of TiO 2 surfaces have revealed spectra much like those depicted in Figure 5a and b, with the spectra varying considerably depending on the past history of the TiO 2 and subsequent treatments.…”

Section: ■ Discussionmentioning

confidence: 99%

Formation of Self-Assembled Monolayers of π-Conjugated Molecules on TiO₂ Surfaces by Thermal Grafting of Aryl and Benzyl Halides

et al. 2012

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We demonstrate the formation of molecular monolayers of π-conjugated organic molecules on nanocrystalline TiO(2) surfaces through the thermal grafting of benzyl and aryl halides. X-ray photoelectron spectroscopy and Fourier-transform infrared spectroscopy were used to characterize the reactivity of aryl and benzyl chlorides, bromides, and iodides with TiO(2) surfaces, along with controls consisting of nonhalogenated compounds. Our results show that benzyl and aryl halides follow a similar reactivity trend (I > Br > Cl >> H). While the ability to graft benzyl halides is consistent with the well-known Williamson ether synthesis, the grafting of aryl halides has no similar precedent. The unique reactivity of the TiO(2) surface is demonstrated using nuclear magnetic resonance spectroscopy to compare the surface reactions with the liquid-phase interactions of benzyl and aryl iodides with tert-butanol and -butoxide anion. While the aryl iodides show no detectable reactivity with a tert-butanol/tert-butoxide mixture, they react with TiO(2) within 2 h at 50 °C. Atomic force microscopy studies show that grafting of 4-iodo-1-(trifluoromethyl)benzene onto the rutile TiO(2)(110) surface leads to a very uniform, homogeneous molecular layer with a thickness of ∼0.45 nm, demonstrating formation of a self-terminating molecular monolayer. Thermal grafting of aryl iodides provides a facile route to link π-conjugated molecules to TiO(2) surfaces with the shortest possible linkage between the conjugated electron system and the TiO(2).

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A kinetic study of the mechanisms of S NAr reactions of neutral and cationic metal-complexed halogenoarenes with methoxide ion

Cited by 23 publications

References 1 publication

Ironcyclopentadienyl mediated 2-alkyl-2-arylphenylsulphonylacetonitrile synthesis

Ironcyclopentadienyl mediated 2-alkyl-2-arylphenylsulphonylacetonitrile synthesis

Preparation of Chromium−Manganese Diarene Heterobimetallic Complexes Using a Mn(CO)₃⁺ Transfer Reaction

Formation of Self-Assembled Monolayers of π-Conjugated Molecules on TiO₂ Surfaces by Thermal Grafting of Aryl and Benzyl Halides

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A kinetic study of the mechanisms of S NAr reactions of neutral and cationic metal-complexed halogenoarenes with methoxide ion

Cited by 23 publications

References 1 publication

Ironcyclopentadienyl mediated 2-alkyl-2-arylphenylsulphonylacetonitrile synthesis

Ironcyclopentadienyl mediated 2-alkyl-2-arylphenylsulphonylacetonitrile synthesis

Preparation of Chromium−Manganese Diarene Heterobimetallic Complexes Using a Mn(CO)3+ Transfer Reaction

Formation of Self-Assembled Monolayers of π-Conjugated Molecules on TiO2 Surfaces by Thermal Grafting of Aryl and Benzyl Halides

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Product

Resources

About

Preparation of Chromium−Manganese Diarene Heterobimetallic Complexes Using a Mn(CO)₃⁺ Transfer Reaction

Formation of Self-Assembled Monolayers of π-Conjugated Molecules on TiO₂ Surfaces by Thermal Grafting of Aryl and Benzyl Halides