(η6-Arene)tricarbonylchromium and (η5-cyclohexadienyl) tricarbonylmanganese complexes: indirect nucleophilic substitutions

Rose‐Munch, Françoise; Gagliardini, Vanessa; Renard, Christophe; Rose, Éric

doi:10.1016/s0010-8545(98)00078-2

Cited by 67 publications

(29 citation statements)

References 106 publications

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“…In 1998, F. Rose-Munch et al summarized 1 the achievements on indirect nucleophilic substitution in arenetricarbonylchromium and cationic arenetricarbonylmanganese complexes presenting several examples of cine-and tele-substitutions, as well the first example of cine-and tele-substitution in neutral cyclohexadienyltricarbonylmanganese complex (119 references). A long review, titled "Transition-MetalMediated Dearomatization Reactions" 2 , that appeared two years later only briefly mentioned cine-and telesubstitutions in arenetricarbonylchromium complexes, noting that both reactions probably involved the following sequence of reactions: nucleophilic addition, protonation, isomerization and elimination to reconstruct aromatic system (4 references).…”

Section: Introductionmentioning

confidence: 99%

cine- and tele-Substitution reactions: review of work from 2002-2016

Suwiński¹

2017

Arkivoc

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This report brings new facts and achievements on the cine-and tele-substitutions reactions published in the last fifteen years. The reactions occurred primarily in such systems as nitroarenes, metal homoarene complexes, and five-or six-membered heteroarenes. Sometimes similar reactions were also observed in other systems, including non-aromatic. cine-and tele-Substitution reactions are presented here independently of their mechanisms.

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Section: Introductionmentioning

confidence: 99%

cine- and tele-Substitution reactions: review of work from 2002-2016

Suwiński¹

2017

Arkivoc

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“…[4][5][6] Since then, palladium-catalyzed processes at π-bond ligands in the presence of Cr(CO) 3 groups have been developed. [7] As part of our current studies on organochromium complexes [8,9] and on cross-coupling reactions, [10,11] we were interested in the preparation of tricarbonyl-η 6 -[(thiophenyl)arene-and -(thiophenyl)carbonylarene]chromium complexes by using a bimetallic activation. This paper describes how the judicious choice of reaction conditions can lead to exceptional selectivities in this class of bond-formation reactions.…”

Section: Introductionmentioning

confidence: 99%

Tricarbonyl-η6-[(2-thiophenyl)arene]- and -η6-[(2-thiophenyl)carbonylarene]- chromium Complexes: Preparation and Conformational Study

Prim

Tranchier

Rose‐Munch

et al. 2000

Eur. J. Inorg. Chem.

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The cross coupling reaction of (p‐chloroanisole)tricarbonylchromium complex (1) with thiophene derivatives under palladium‐catalyzed conditions leads to the selective formation of tricarbonyl‐η6‐[(2‐thiophenyl)arene]‐ or ‐η6‐[(2‐thiophenyl)carbonylarene]chromium complexes (2 or 3) depending on reaction conditions. The conformation of complexes 2 and 3 in the solid state as well as in solution are reported.

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“…add to the ipso carbon of (haloarene)Cr(CO) 3 providing an intermediate (9: M=Cr(CO) 3 , Scheme 2) which upon loss of the leaving group gives a substituted complex 10: M= Cr(CO) 3 . Unstabilized nucleophiles (e.g., sulfur-stabilized alkyllithium reagents) give a kinetic addition product (e.g., 11: M=Cr(CO) 3 -) which does not rearrange to 9 and therefore can give substitution only by loss of a leaving group by a different mechanism, as will be discussed later.…”

Section: (Halobenzene)cr(co) 3 Complexesmentioning

confidence: 99%

“…If a hydrogen occupies the ipso position, oxidation of the intermediate gives formal nucleophilic substitution for hydrogen (3, path b). General reviews have appeared [1][2][3][4] as well as others with an emphasis on h 6 -arene-Cr(CO) 3 complexes [5,6], on h 6 -arene-FeCp + (Cp=h 5 -cyclopentadienyl) complexes [7][8][9], h 6 -arene-RuCp + [10,11], and on h 6 -arene-Mn(CO) 3 complexes [12]. The purpose of this chapter is to summarize the established or potential synthesis methodology available via nucleophile addition to a metal-coordinated arene ligand.…”

Section: Introductionmentioning

confidence: 99%

“…1): neutral h 6 -arene-Cr(CO) 3 (4), cationic (h 6 -arene)(h 5 -cyclopentadienyl)Fe(II) (5) and (h 6 -arene)(h 5 -cyclopentadienyl)Ru(II) (6), cationic h 6 -arene-Mn(CO) 3 (7), and the dicationic (h 6 -arene)(h 5 -ethyltetramethylcyclo-pentadienyl)Rh(III) complexes (8). For the series Cr, Mo, and W, the nature of the metal has little effect on rate of nucleophile addition, while for Fe, Ru, and Os, the reactivity decreases with increasing atomic number [4].…”

Section: Introductionmentioning

confidence: 99%

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(Arene)Cr(CO)3 Complexes: Aromatic Nucleophilic Substitution

Semmelhack

Chlenov

2004

Topics in Organometallic Chemistry

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Transition metals coordinated to the pi system of arenes function as strong electronwithdrawing groups and favor nucleophilic addition to the arene to give cyclohexadienyl-metal complexes. The regioselectivity of addition is influenced in subtle and indirect ways, compared to the powerful effect on both reactivity and regioselectivity of electron-withdrawing groups attached to the sigma bond system of the arene. The intermediate cyclohexadienyl complexes can be processed in several ways, leading to several distinct synthesis methods. Useful reactivity is known for several metal systems and each is discussed for specific reaction types. The presence of a fluoro or chloro substituent on the arene allows an effective analog of classical S N Ar reactivity, with a wide range of nucleophiles including simple amines, alkoxides, and carbon anions. Another general process is the addition/protonation protocol, where a hydrogen substituent on the arene is replaced by a nucleophile. This opens new questions of regioselectivity since the typical arene ligand has several hydrogens which are candidates for substitution. The formation of five-and six-membered rings by both general mechanisms are known. Less general indirect mechanisms (e.g., tele substitution) have also been defined.

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(η6-Arene)tricarbonylchromium and (η5-cyclohexadienyl) tricarbonylmanganese complexes: indirect nucleophilic substitutions

Cited by 67 publications

References 106 publications

cine- and tele-Substitution reactions: review of work from 2002-2016

cine- and tele-Substitution reactions: review of work from 2002-2016

Tricarbonyl-η6-[(2-thiophenyl)arene]- and -η6-[(2-thiophenyl)carbonylarene]- chromium Complexes: Preparation and Conformational Study

(Arene)Cr(CO)3 Complexes: Aromatic Nucleophilic Substitution

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