Regioselektive Metallierung von Aromaten, II. Zweitmetallierung von 1‐Lithionaphthalin und 9‐Lithioanthracen

Neugebauer, Wolfgang; Clark, Timothy; Schleyer, Paul von Ragué

doi:10.1002/cber.19831161003

Cited by 57 publications

(26 citation statements)

References 30 publications

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“…Thallium hexafluorophosphate was purchased from Alfa Aesar. 1,8-Dilithionaphthalene-tmeda [10] and triphenyldibromoantimony [21] were prepared according to published procedures. All preparations were carried out under an atmosphere of dry N 2 employing either a glove box or standard Schlenk techniques.…”

Section: Methodsmentioning

confidence: 99%

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A Mercury→Antimony Interaction

et al. 2010

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Section: Methodsmentioning

confidence: 99%

“…[9] Reaction of 1,8-dilithionaphthalene [10] with Ph 3 SbBr 2 in THF followed by addition of HgBr 2 afforded 1 as a yellow solid in 54 % yield (Scheme 1). This compound could be converted into the corresponding hexafluorophosphate salt 2-PF 6 by abstraction of the bromide anion with TlPF 6 .…”

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confidence: 99%

A Mercury→Antimony Interaction

et al. 2010

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“…The reaction of 1,8-dilithionaphthalene·TMEDA [8] with two molar equivalents of 4,4-dimethoxybenzophenone affords the corresponding diol, namely 1,8-bis[bis(p-methoxyphenyl)hydroxymethyl]naphthalene (1) (Scheme 1). Upon treatment with a mixture of aq [HBF 4 ] and (CF 3 CO) 2 O, this diol undergoes a double dehydroxylation reaction to afford the corresponding dication, 2 2+ (Scheme 1).…”

Section: Arene Electrochemistrymentioning

confidence: 99%

Synthesis and Reactivity of a 1,8‐Bis(methylium)naphthalenediyl Dication

Wang

Gabbaı̈

2003

Angew Chem Int Ed

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The enforced proximity of the methylium centers in 1,8-bis(bis(p-methoxyphenyl)methylium)-naphthalenediyl dication makes them cooperate and ultimately magnifies the electron affinity of this molecule. Like the carnivorous plant Dionaea traps flies, this dication readily captures electrons and then holds them in a newly formed carbon-carbon bond. For more information on this chemistry, see the following Communication by

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“…1,8-dibromonaphthalene N13 and 5,6-dibromoacenaphthene A13 both readily undergo lithium-halogen exchange reactions to form mono-and di-lithiated precursors for many metal-substitution reactions, and have previously been shown to react with diphenyl dichalcogenides to form substituted chalcogen compounds. [17,18,30,31] 13 was initially prepared following a modified version of the route reported by Meinwald and Chiang. [28] A chloroform solution of 5,6-dibromoacenaphthene A13 [32] was treated with 2.2 equivalents of N-bromosuccinimide (NBS) and 0.22 equivalents of benzoyl peroxide and heated under reflux for five hours affording A0 (yield 74%).…”

Section: ]mentioning

confidence: 99%

Bridging the Gap: Attractive 3c–4e Interactions in peri‐Substituted Acenaphthylenes

et al. 2014

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Keywords: acenaphthylene /peri-substitution /3c-4e interaction /X-ray crystallography / DFT calculations/non-covalent A series of peri-substituted acenaphthylenes containing mixed halogen-chalcogen functionalities at the 5,6-positions in 1-6 (Acenapyl [X][EPh] (Acenap = acenaphthylene-5,6-diyl; X = Br, I; E = S, Se, Te) and chalcogen-chalcogen moieties in 7-11 (Acenap [EPh][E`Ph] (Acenap = acenaphthene-5,6-diyl; E/E` = S, Se, Te), have been prepared from their corresponding acenaphthene analogues A1-A11, utilizing 2,3-dichloro-5,6-dicyano-1,4-benzoquinone (DDQ) for the dehydrogenation of the ethane backbone. The related dihalide compounds 13 and 14 Acenapyl[XX`] (XX` = BrBr, II) have also been prepared following a similar procedure and 1,2,5,6-tetrabromo-1,2-dihydroacenaphthylene A0 was prepared as an intermediate following an alternative route to 13. The series of acenaphthylene compounds have remarkably similar molecular structures to their acenaphthene counterparts, exhibiting an expected increase in periseparation as heavier congeners occupy the close peri-positions.The presence of the ethene bridge, however, naturally compresses the nearest bay angle whilst increasing the splay of the exocyclic peri-atoms, resulting in a minor increase in separation compared with equivalent acenaphthenes. The structures of 1-11, 13 and 14 are discussed and compared with previously reported analogous naphthalene and acenaphthene compounds. Similar to acenaphthene derivatives, aromatic ring conformations and the location of p-type lone-pairs influences the geometry of the peri-region. Under appropriate geometric conditions quasi-linear three-body C Ph -E···Z (E = Te, Se, S; Z = Br/E) fragments provide an attractive component for the E···Z interaction. DFT studies confirm the onset of formation of threecenter, four-electron bonding, similar in extent as observed in analogous acenaphthenes, despite an increase in the peridistances. IntroductionUnderstanding how atoms interact in different bonding situations and the ability to quantify the extent of bonding between two atoms is an ongoing challenge for chemists, and one which dates back to the origins of the electronic theory of valence proposed by Lewis and Langmuir in the early 1900s. [1,2] The stability of molecules was originally ascribed to their ability to pair valence electrons off in chemical bonds to achieve 'stable octets', with the concept of covalence introduced as 'the number of pairs of electrons an atom can share with its neighbor'. [1][2][3] Ambiguity over the bonding in molecules of heavier main-block elements (period 3 and higher), in which an 'octet expansion' would be required in order to conform to conventional Lewis 2c-2e covalent bonding theory, was thus rationalized by the availability of unfilled low-lying d-orbitals. [1] Langmuir, however, accounted for the legitimacy of the octet rule by suggesting the bonding in these species, termed hypervalent, [4] was now ionic rather than covalent in nature. [2] The advancement of molecular orbital theory in t...

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Regioselektive Metallierung von Aromaten, II. Zweitmetallierung von 1‐Lithionaphthalin und 9‐Lithioanthracen

Cited by 57 publications

References 30 publications

A Mercury→Antimony Interaction

A Mercury→Antimony Interaction

Synthesis and Reactivity of a 1,8‐Bis(methylium)naphthalenediyl Dication

Bridging the Gap: Attractive 3c–4e Interactions in peri‐Substituted Acenaphthylenes

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