Nucleophilic Aromatic Addition Reactions of the Metallabenzenes and Metallapyridinium: Attacking Aromatic Metallacycles with Bis(diphenylphosphino)methane to Form Metallacyclohexadienes and Cyclic η<sup>2</sup>‐Allene‐Coordinated Complexes

Zhang, Hong; Lin, Ran; Hong, Gang; Wang, Tongdao; Wen, Ting Bin; Xia, Haiping

doi:10.1002/chem.201000324

Cited by 42 publications

(27 citation statements)

References 95 publications

(30 reference statements)

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“…Since these early reports the study of metallabenzenes has flourished. [39][40][41][42][43][44] The third row transition metalsa re well-represented with examples incorporating osmium, [45][46][47][48][49][50][51][52][53][54][55][56][57][58][59][60][61] iridium, [62][63][64][65][66][67][68][69][70][71][72][73][74][75][76][77][78][79][80] platinum [81][82][83][84] and, most recently,r henium. [85][86][87] Metallabenzenes of one second row transition metal, ruthenium, are also known.…”

Section: Metallabenzenesmentioning

confidence: 99%

“…Nitration or bromination occurs at the C4 position, para to the -SMe substituent, following normal aromatic directing effects (see (a), Scheme 3). [45,77] Other "benzene-like" reactions that have been observed for metallabenzenes include nucleophilic aromatic substitution of hydrogen [52,54,92] (Scheme 3see (b)) nucleophilic aromatic addition to the ring, [57,66,94] and p-complexation to suitable metal substrates [84,[106][107][108] (Scheme 3see (c)). The reactions of metallabenzenes, however, do not always follow those classically observed for benzene.…”

Section: Metallabenzenesmentioning

confidence: 99%

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Recent Advances in Metallaaromatic Chemistry

Frogley

Wright

2017

Chemistry A European J

141

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Metallaaromatics can be broadly defined as aromatic compounds in which one of the ring atoms is a transition metal. The metallabenzenes are one important class of these compounds that has undergone extensive study recently. Closely related species such as fused-ring metallabenzenes, heterometallabenzenes, π-coordinated metallabenzenes and metallabenzynes have also attracted considerable attention. Although many metallaaromatics can be considered as metalla-analogues of classic organic aromatic compounds, this is not always the case. Recent seminal studies have shown that metallapentalenes and metallapentalynes, which are metalla-analogues of the anti-aromatic compounds pentalene and pentalyne, are in fact aromatic and highly stable. Very unusual spiro-metallaaromatic compounds have also recently been isolated. In this concepts article, key features of all these intriguing metallaaromatic compounds are discussed with reference to the structural, spectroscopic, reactivity and theoretical studies that have been undertaken. These compounds continue to generate much interest, not only because of the contributions they make to fundamental chemical understanding, but also because of the promise of possible practical applications.

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Section: Metallabenzenesmentioning

confidence: 99%

Section: Metallabenzenesmentioning

confidence: 99%

Recent Advances in Metallaaromatic Chemistry

Frogley

Wright

2017

Chemistry A European J

141

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“…[12] Many interesting chemical properties of metallabenzenes have also been discovered. For example, it has been demonstrated that metallabenzenes can undergo electrophilic substitution reactions, [2a, 5d] cycloaddition reactions, [8d, 9c] nucleophilic addition reactions, [13] and nucleophilic aromatic substitution of hydrogen. [14] Another common reactivity of metallabenzenes is that they can undergo migratory insertion reactions to give cyclopentadienyl complexes.…”

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confidence: 99%

Conversion of Metallabenzynes into Carbene Complexes

et al. 2011

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The chemistry of transition metal-containing metallabenzenes has attracted considerable attention.[1] Previous studies have led to the isolation and characterization of a number of stable metallabenzenes, especially those of osmium, [2][3][4] iridium, [5][6][7][8] platinum, [9] ruthenium, [10,11] and rhenium. [12] Many interesting chemical properties of metallabenzenes have also been discovered. For example, it has been demonstrated that metallabenzenes can undergo electrophilic substitution reactions, [2a, 5d] cycloaddition reactions, [8d, 9c] nucleophilic addition reactions, [13] and nucleophilic aromatic substitution of hydrogen. [14] Another common reactivity of metallabenzenes is that they can undergo migratory insertion reactions to give cyclopentadienyl complexes. The transformation has been demonstrated with well-characterized metallabenzenes [2e, 6b,-d,e, 10b] as well as a spectroscopically characterized ruthenabenzene, [15] and it has been proposed as a key step in the formation of cyclopentadienyl complexes.[1]Compounds closely related to metallabenzenes are metallabenzynes.[16] Compared with the chemistry of metallabenzenes, that of metallabenzynes is much less developed, which is partly due to the lack of convenient methods to synthesize such compounds.[17] Structurally, metallabenzynes are similar to metallabenzenes in that both have a delocalized structure. Thus it might be expected that metallabenzynes should have properties similar to those of metallabenzenes. Indeed, previous studies have demonstrated that metallabenzynes, like metallabenzenes, can also undergo electrophilic substitution reactions [18] and nucleophilic addition reactions.[17c] As formation of cyclopentadienyl complexes from metallabenzenes by migratory insertion reactions is well-known, one might expect that metallabenzynes could also undergo migratory insertion reactions to give carbene complexes. However, such reactions have not been previously observed. Herein, we present a reliable method to prepare osmabenzynes along with the first examples of conversion of metallabenzynes into carbene complexes.We recently observed that reaction of zinc with the osmium vinyl carbyne complex [OsCl 3 { C À CH = C(2-ClC 6 H 4 ) 2 }(PPh 3 ) 2 ] produced a osmanaphthalyne complex. [19] The reaction was proposed to proceed through a 16e fourcoordinate square planar osmium carbyne complex, which undergoes an oxidative addition reaction involving a CÀCl bond. Inspired by the observation, we envisioned that reactions of zinc with carbyne complexes of the type [OsCl 3 { C À CH = CR À CR' = CClR''}(PPh 3 ) 2 ] might lead to the formation of new osmabenzynes.To test this hypothesis, we first prepared the meridional osmium carbyne complex 1 and then treated it with zinc in THF at room temperature. An in situ 31 P NMR study showed that osmabenzyne 2 with substituents on the C3 and C5 positions was produced as the major phosphorus-containing product (Scheme 1), which can be isolated in 62 % yield after column chromatography.The osmabenzyne 2 has bee...

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“…Furthermore, allene-containing phosphines have been characterized as ligands for Fe 26 and Os. 27 However, this study is the first to demonstrate that optically active allenes can coordinate to transition metals and maintain their stereochemical integrity. These observations suggested they might represent effective ligands for asymmetric catalysis.…”

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confidence: 81%

Chiral Allene-Containing Phosphines in Asymmetric Catalysis

Cai

et al. 2011

J. Am. Chem. Soc.

152

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Traditionally, ligands used in asymmetric catalysis have contained either stereogenic atoms or hindered single bonds (atropisomerism), or both. Here we demonstrate that allenes, chiral 1,2-dienes, appended with basic functionality can serve as ligands for transition metals. We describe an allene-containing bisphosphine that, when coordinated to Rh(I), promotes the asymmetric addition of aryl boronic acids to α-keto esters with high enantioselectivity. Solution and solid-state structural analysis reveals that one olefin of the allene can coordinate to transition metals generating bi- and tri-dentate ligands.

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Nucleophilic Aromatic Addition Reactions of the Metallabenzenes and Metallapyridinium: Attacking Aromatic Metallacycles with Bis(diphenylphosphino)methane to Form Metallacyclohexadienes and Cyclic η²‐Allene‐Coordinated Complexes

Cited by 42 publications

References 95 publications

Recent Advances in Metallaaromatic Chemistry

Recent Advances in Metallaaromatic Chemistry

Conversion of Metallabenzynes into Carbene Complexes

Chiral Allene-Containing Phosphines in Asymmetric Catalysis

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Nucleophilic Aromatic Addition Reactions of the Metallabenzenes and Metallapyridinium: Attacking Aromatic Metallacycles with Bis(diphenylphosphino)methane to Form Metallacyclohexadienes and Cyclic η2‐Allene‐Coordinated Complexes

Cited by 42 publications

References 95 publications

Recent Advances in Metallaaromatic Chemistry

Recent Advances in Metallaaromatic Chemistry

Conversion of Metallabenzynes into Carbene Complexes

Chiral Allene-Containing Phosphines in Asymmetric Catalysis

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Product

Resources

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Nucleophilic Aromatic Addition Reactions of the Metallabenzenes and Metallapyridinium: Attacking Aromatic Metallacycles with Bis(diphenylphosphino)methane to Form Metallacyclohexadienes and Cyclic η²‐Allene‐Coordinated Complexes