Reaction of ferrocene with polyaromatic molecules. .pi.-Arene bis((.pi.-cyclopentadienyl)iron) dications. I. Molecular structures

Morrison, William H.; Ho, Ellen Y.; Hendrickson, David N.

doi:10.1021/ja00818a038

Cited by 72 publications

(14 citation statements)

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“…From Table 1, it is seen that in agreement with earlier observations (8, 9, 1 I), the aromatic ring, after complexing with the CpFe group, shows a n upfield shift as was first reported by Hendrickson 'The endo and exo designations are used to indicate that the H atoms at C-9,10 and the CpFe group are on the same side and on opposite sides, respectively, of the ring system (13 and co-workers (8). With regard to the stereochemistry of the hydrogenation, it is of interest to note that for ion 100, in which the H atoms at C-9,lO are cwdo or on the same side of the ring system as the CpFe group, the CH, and C-9,lO absorptions are quite similar for 100 and the hydrogenated ligand 11.…”

Section: Discussionsupporting

confidence: 86%

“…In the present work, ligand exchange reactions between FcH and 9,lOdimethylanthracene, in the presence of AIC1,-AI, were studied with the view of elucidating the stereochemical nature and hence the probable mechanism for the hydrogenation process observed in such reactions. (8) can be readily prepared in a one-step reaction from vinyl acetate, AICI,, and benzene (12). By analogy with the ready formation of the 9,lO-dihydroanthracene complex 6 from anthracene, it may be anticipated that if hydrogenation occurs in the ligand exchange reaction between FcH and 8, the hydrogenation could be specifically tl.ans to give ion 9, specifically cis and endo t o the CpFe group to give ion 10a, and specifically cis and exo to the CpFe group t o give ion lob,' or hydrogenation might take place randomly to give a mixture of these isomers.…”

Section: Cpmentioning

confidence: 99%

“…moieties were shown to be trans t o each other (3). Subsequently, Hendrickson and co-workers (8) reported the synthesis of a number of such dications from a variety of aromatic polynuclear hydrocarbons. However, we have found that such re- example, reaction of naphthalene with ferrocene (FcH)-AIC1,-A1 gave rise to both the q6-naphthalene-q5-cyclopentadienyliron cation (4) and the i16-tetralin-q5-cyclopentadienyliron cation (5), whereas anthracene gave only the hydrogenated q6-9, 10-dihydroanthracene-q5-cyclopentadienyliron cation (6) and the corresponding dication (7) (9).…”

Section: Introductionmentioning

confidence: 99%

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Ligand exchange reactions between ferrocene and 9,10-dimethylanthracene

Sutherland¹,

Pannekoek²,

Lee³

1978

Can. J. Chem.

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RONALD G . SUTHERLAND, W. JACK PANNEKOEK, and C~o r CHUCK LEE. Can. J. Chern. 56, 1782Chern. 56, (1978.The reaction of 9,IO-dimethylanthracene (8) with ferrocene (FcH) in the presence of AICI,-AI in decalin gave the stereospecifically hydrogenated product, i16-cis-(endo-9,10-dihydro)-9,10-dimethylanthracene-q5-cyclopentadienyliron cation (loo), the hydrogenation at C-9,10 being cis and endo o r on !he same side as the cyclopentadienyliron (CpFe) moiety. When cis-9,lOdihydro-9,lO-dimethylanthracene, generated from 10a by photolysis o r pyrolytic sublimation, was used a s the arene in the ligand exchange reaction, complexing with the CpFe group could occur from either side of the ring system, giving rise to a mixture o f 10a and the q6-cis-(exo-9,10-dihydro)-9,l0-dimethylanthracene-~-cyclopentadienyliron cation (lob). The q6-cis-9,10-dihydro-9,10-dimethylanthracene-trnt1s-bis-q~-cyclopentadienyliron dication, with the two CpFe groups tratw, was also prepared either from a stepwise ligand exchange using 100 or directly from reaction of 8 using an excess of FcH. A mechanism is proposed for the hydrogenation that has been found to accompany ligand exchange reactions between polycyclic arenes and F c H and possible applications are pointed out for the synthesis of partially hydrogenated polycyclic aromatic hydrocarbons. Chem. 56, 1782Chem. 56, (1978.La reaction du dimethyl-9,lO anthracene (8) avec le ferrocene (FcH) en presence de AIC1,-A1 dans la decaline conduit a un produit hydrogent stereospCcifiquement soit le cation 11" (dihydro-9,10 et~&) dimethyl-9,10 anthracene q 5 cyclopentadienylfer cis (Ion), I'hydrogtnation au niveau des atomes d e carbone 9,10 se faisant cis et endo, soit sur le m&me c8te que la portion cyclopentadienylfer (CpFe). Lorsque I'on utilise du dihydro-9,lO dimethyl-9,lO anthracene cis, produit a partir d e 100 par photolyse ou sublimation pyrolytique, comme arene d a n s la reaction d'kchange de ligand, la complexation avec le groupe CpFe pourrait se produire de chaque c8tC du systeme cyclique et pourrait conduire a un melange de 100 et d u cation q" (dihydro-9,10 eso) dimethyl-9,lO anthracene q 5 cyclopentadienylfer cis (lob). On a aussi prepark le dication q6 dihydro-9,10 dimethyl-9,10 anthracene cis bis-q5 cyclopentadihylfer trans avec les deux groupes C p F e tratls; on a prepare ce compose soit par un echange par etape du ligand faisant appel a 100 soit directement par reaction de 8 avec un exces de F c H . On propose un mecanisme pour I'hydrogenation qui accompagne les reactions d'echange de ligand entre les arenes polycycliques et FcH et on indique des applications possibles p o u r la synthese d'hydrocarbures aromatiques polycycliques partiellement hydrogenes.[Traduit par le journal]

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Section: Discussionsupporting

confidence: 86%

Section: Cpmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Ligand exchange reactions between ferrocene and 9,10-dimethylanthracene

Sutherland¹,

Pannekoek²,

Lee³

1978

Can. J. Chem.

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“…Grafting of polymers onto GO by ligand-exchange reaction with ferrocene 3.1. Ligand-exchange reaction of ferrocene with graphene structure of nanocarbons Morrison et al reported that the h 6 -benzene-h 5 -cyclopentadienyliron cation could be readily prepared by the ligand-exchange reaction of ferrocene with benzene in the presence of AlCl 3 and Al powders as the catalysts [31,32]. Furthermore, Miyake et al reported that the ligand-exchange reaction is successfully applied for the introduction of functional groups to graphene structure of various carbon materials [32].…”

Section: Identification Of Peg Grafting Onto Go By Gc-msmentioning

confidence: 99%

A Novel Grafting of Polymers onto the Surface of Graphene Oxide

Tsubokawa¹,

Yamauchi²,

Fujiki³

et al. 2017

Graphene Materials - Structure, Properties and Modifications

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A simple grafting of polymers onto graphene oxide (GO) was achieved by polymer radical trapping, ligand-exchange reaction, and surface initiated cationic and anionic graft polymerization. Grafting of poly(ethylene glycol) (PEG) onto GO was successfully achieved by trapping of PEG radicals formed by thermal decomposition of PEG macroazo initiator to give PEG-grafted GO. The grafting of copolymers containing vinyl ferrocene moieties onto GO surfaces was also successfully achieved by the ligand-exchange reaction between ferrocene moieties of these copolymers and GO. Carboxyl groups on GO have an ability to initiate the cationic polymerizations of vinyl monomers, such as N-vinylcarbazole and isobutyl vinyl ether. The corresponding vinyl polymers were grafted onto GO, during the cationic polymerization, based on the termination of growing polymer cation by counter anion (carboxylate) groups on GO. It was found that the anionic ring-opening alternating copolymerization of epoxides with cyclic acid anhydrides was successfully initiated by potassium carboxylate groups on GO, introduced by neutralization of carboxyl groups with KOH, to give the corresponding polyester-grafted GO. The dispersibility of GO in organic solvents was remarkably improved by the grafting of the above polymers onto GO. In addition, easy preparation of reduced GO-based conducting polyaniline composite organogel will be discussed.

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“…Ein Ligandenaustausch in Ferrocenen mit Aromaten wurde zuerst von NESMEYANOV und Mitarbeitern 1 beobachtet und ist anschließend auch von anderen Arbeitsgruppen untersucht worden [2][3][4] .…”

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