An investigation of the formation of 1,3,5-heterosubstituted benzene rings by cyclo-condensation of acetyl-substituted organometallic complexes

Ogini, Francis O.; Ortin, Yanick; Mahmoudkhani, Amir; Cozzolino, Anthony F.; McGlinchey, Michael J.; Vargas‐Baca, Ignacio

doi:10.1016/j.jorganchem.2008.02.013

Cited by 11 publications

(7 citation statements)

References 80 publications

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“…[17] Moreover,arecent study on the protonation of acetylferrocene, [Fe{C 5 H 4 ÀC(=O)CH 3 }(C 5 H 5 )],a nd acetylcymantrene, [Mn{C 5 H 4 ÀC(=O)CH 3 }(CO) 3 ], revealed the ferrocenyl-stabilised system to be favoured. [18] In ap reviouss tudy from this laboratory,v ariable-temperature 31 PNMR spectroscopyd ata on the cluster-stabilised fluorenyl 10 b,2 ,3-diphenylindenyl 11 b and tetraphenylcyclopentadienyl 12 b clusterc ations (Scheme 5) revealed that the barrier to migration of the cationic centre between cobalt vertices Scheme2.In situ generationo facarbocation over am etal cluster:(a) h 2 coordinationoft he C=C p linkageformed at the expense of aC o ÀC alkynyl electron pair;( b) alleviation of the carbocationic chargeb yelectronic donation from af illed cobalt d z 2 orbital.…”

Section: Introductionmentioning

confidence: 99%

“…Other studies reveal that a phosphane ligand enhances the basicity of the [Co(CO) 2 (Ph 3 P)] fragment over the [Co(CO) 3 ] moiety, hence favouring correspondingly better Co–C interactions . Moreover, a recent study on the protonation of acetylferrocene, [Fe{C 5 H 4 −C(=O)CH 3 }(C 5 H 5 )], and acetylcymantrene, [Mn{C 5 H 4 −C(=O)CH 3 }(CO) 3 ], revealed the ferrocenyl‐stabilised system to be favoured …”

Section: Introductionmentioning

confidence: 99%

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[Co₂(CO)₆(Alkynyl)] Complexes of Dibenzosuberyl and Dibenzosuberenyl Carbocations: Dibenzotropylium or Dibenzoheptafulvene?

et al. 2016

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The reaction of dibenzo[a,d]cycloheptan‐5‐one (dibenzosuberone) and dibenzo[a,d]cyclohept‐10‐en‐5‐one (dibenzosuberenone) with aryl‐ or trimethylsilylacetylides led to the formation of the corresponding alkynyldibenzosuberols and alkynyldibenzosuberenols. Treatment with dicobalt octacarbonyl and then with bis(diphenylphosphino)methane (dppm) furnished the corresponding [Co2(CO)4(dppm)(alkynol)] clusters 25 and 29. Upon protonation with HBF4 at 203 K to generate the relevant cobalt‐stabilised cations, the dibenzosuberyl system 30 exhibited fluxionality such that the cation migrated between cobalt centres. Variable‐temperature 31P NMR spectroscopy revealed a barrier of approximately 12.5 kcal mol−1. In contrast, in the supposedly aromatic [Co2(CO)4(dppm)(dibenzosuberenyl)]+ cation (31), which would be expected to have less need of cobalt stabilisation, the barrier was too high to be measured experimentally, but is certainly in excess of 16 kcal mol−1. These data were rationalised by DFT calculations on the structures and energies of the relevant ground states and transition states, which suggested that the nonplanar alkynyldibenzosuberenyl moiety in 31 is better regarded as a neutral dibenzoheptafulvene coordinated to a cationic alkynyl–dicobalt cluster. The question of the bonding of both aromatic and antiaromatic cations to alkyne–dicobalt clusters is considered, and it is proposed that their stabilities, when complexed, parallel the inversion of (4n+2) π and 4n π systems seen under photochemical conditions.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

[Co₂(CO)₆(Alkynyl)] Complexes of Dibenzosuberyl and Dibenzosuberenyl Carbocations: Dibenzotropylium or Dibenzoheptafulvene?

et al. 2016

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“…This is a general reaction and has also been exploited in the case of (acetylcyclopentadienyl)manganesetricarbonyl which, likewise, yields the 1,3,5-trisubstituted aromatic [17]. Moreover, mixed species are also accessible, as typified by the Fe2Mn example, 36, shown in Figure 2; indeed, the bimetallic Fe-Mn precursor, 37, corresponding to 33 in Scheme 7 has also been characterized by Xray crystallography [20]. This approach has also been used to prepare C3h-symmetric polycyclic systems [17].…”

Section: Ferrocene-mediated Cyclization To Form Trisubstituted Aromat...mentioning

confidence: 95%

Ferrocenyl Migrations and Molecular Rearrangements: The Significance of Electronic Charge Delocalization

McGlinchey

2020

Inorganics

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The enhanced stabilization of a carbocationic site adjacent to a ferrocenyl moiety was recognized within a few years of the discovery of sandwich compounds. While a detailed understanding of the phenomenon was the subject of some early debate, researchers soon took advantage of it to control the ease and direction of a wide range of molecular rearrangements. We, here, discuss the progress in this area from the pioneering studies of the 1960s, to more recent applications in chromatography and analytical detection techniques, and currently in the realm of bioactive organometallic complexes. Several classic reactions involving ferrocenyl migrations, such as the pinacol, Wolff, Beckmann, and Curtius, are discussed, as well as the influence of the ferrocenyl substituent on the mechanisms of the Nazarov, Meyer-Schuster, benzoin, and Stevens rearrangements. The preparation and isomerizations of ferrocenyl-stabilized vinyl cations and vinylcyclopropenes, together with the specific cyclization of acetylcyclopentadienyl-metal derivatives to form 1,3,5-substituted benzenes, demonstrate the versatility and generality of this approach.

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“…8 In this work, we calculated the first 40 transitions of 4 and 5, used these to model the total absorption spectra, and identified the main contributions to the lowest three bands of each compound. There was good agreement in the shape and relative intensity of the bands, although their l max was underestimated by up to 45 nm.…”

Section: C(o)h)] and [(C 5 H 5 )Fe(c 5 H 4 C(oh)h)] + The First Banmentioning

confidence: 99%

“…7 Indeeed, the pK a values of [(CO) 3 Mn(C 5 H 4 -C(OH)-CH 3 )] + and [(C 5 H 5 )Fe(C 5 H 4 -C(OH)-CH 3 )] + (1) are -4.0 and -2.6, respectively. 8 Such protonated species are considered key intermediates in the acid-catalyzed oligomerization of the ketones, 9 which yields 3,1 disubstituted (E)-2-buten-1-ones (2) and 1,3,5-trisubstituted benzenes (3). The relative yields of the heterometallic condensation products from mixtures of acetylferrocene (4) and acetylcymantrene has been rationalized by considering the relative stabilities of those cations.…”

Section: Introductionmentioning

confidence: 99%

An investigation of (C₅H₅)Fe(C₅H₄–C(OBF₃)–CH₃)^,

et al. 2009

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Acetylferrocene readily forms an adduct with BF 3 . The product is a neutral model for protonated acetylferrocene, a species that is a crucial intermediate in the formation of 1,3,5-trisferrocenyl-benzene and other conjugated heterometallic derivatives by cyclocondensation. The title compound's structure was determined in the solid state by X-ray diffraction and its spectroscopic properties were examined in detail, particularly the electronic excitation spectrum, which confirms the previous identification of the in situ generated protonated ketone.Résumé : L'acétylferrocène forme facilement un adduit avec le BF 3 . Le produit est un modèle neutre pour un acétylferro-cène, une espèce qui est un intermédiaire crucial dans la formation du 1,3,5-trisferrocényl-benzène et d'autres dérivés hété-rométalliques par cyclocondensation. La structure du composé mentionné dans le titre a été déterminée à l'état solide par diffraction des rayons X et on a examiné ses propriétés spectroscopiques en détail, en particulier son spectre d'excitation électronique qui confirme l'identification antérieure de la cétone protonée générée in situ.Mots-clés : cétones organométalliques, adduits avec le BF 3 , cations ferrocényles, calculs d'après la théorie de la fonctionnelle de la densité (TFD).[Traduit par la Rédaction]

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An investigation of the formation of 1,3,5-heterosubstituted benzene rings by cyclo-condensation of acetyl-substituted organometallic complexes

Cited by 11 publications

References 80 publications

[Co₂(CO)₆(Alkynyl)] Complexes of Dibenzosuberyl and Dibenzosuberenyl Carbocations: Dibenzotropylium or Dibenzoheptafulvene?

[Co₂(CO)₆(Alkynyl)] Complexes of Dibenzosuberyl and Dibenzosuberenyl Carbocations: Dibenzotropylium or Dibenzoheptafulvene?

Ferrocenyl Migrations and Molecular Rearrangements: The Significance of Electronic Charge Delocalization

An investigation of (C₅H₅)Fe(C₅H₄–C(OBF₃)–CH₃)^,

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An investigation of the formation of 1,3,5-heterosubstituted benzene rings by cyclo-condensation of acetyl-substituted organometallic complexes

Cited by 11 publications

References 80 publications

[Co2(CO)6(Alkynyl)] Complexes of Dibenzosuberyl and Dibenzosuberenyl Carbocations: Dibenzotropylium or Dibenzoheptafulvene?

[Co2(CO)6(Alkynyl)] Complexes of Dibenzosuberyl and Dibenzosuberenyl Carbocations: Dibenzotropylium or Dibenzoheptafulvene?

Ferrocenyl Migrations and Molecular Rearrangements: The Significance of Electronic Charge Delocalization

An investigation of (C5H5)Fe(C5H4–C(OBF3)–CH3),

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[Co₂(CO)₆(Alkynyl)] Complexes of Dibenzosuberyl and Dibenzosuberenyl Carbocations: Dibenzotropylium or Dibenzoheptafulvene?

[Co₂(CO)₆(Alkynyl)] Complexes of Dibenzosuberyl and Dibenzosuberenyl Carbocations: Dibenzotropylium or Dibenzoheptafulvene?

An investigation of (C₅H₅)Fe(C₅H₄–C(OBF₃)–CH₃)^,