Fused-ring metallabenzenes

Frogley, Benjamin J.; Wright, L. James

doi:10.1016/j.ccr.2014.01.019

Cited by 143 publications

(63 citation statements)

References 38 publications

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“…In the 1 H NMR spectra of 5 or 6 , signals for the H1 protons appear at 6.11 or 7.55 ppm, respectively, positions that are considerably further up‐field than in most other metallabenzenes (ca. 10–18 ppm) or metallabenzofurans (ca. 7.7–12.6 ppm) .…”

Section: Resultsmentioning

confidence: 99%

“…Metalla‐analogues of conventional organic aromatic compounds, in which a transition metal and its ancillary ligands formally replace one carbon atom, have attracted considerable interest recently . Although the isolation and study of a considerable number of metallabenzenes and fused‐ring metallabenzenes has been reported, much remains to be explored regarding the reactivity of these compounds. Studies carried out so far have demonstrated that the transition metal modifies significantly the delocalized π‐system and the chemical reactivity compared to the corresponding organic analogues .…”

Section: Introductionmentioning

confidence: 99%

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Syntheses of Amino‐Substituted Iridabenzofurans and Subsequent Selective N‐Functionalisation

Frogley

Perera

Wright

2017

Chemistry A European J

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The first examples of amino-substituted fused-ring metallabenzenes, the cationic iridabenzofuran [Ir(C H O{NH -2}{OMe-7})(CO)(PPh ) ][O SCF ] (5) and neutral analogue Ir(C H {NH -2}{OMe-7})Cl(PPh ) (6), can be prepared by reduction of the corresponding nitro-substituted iridabenzofurans with zinc and concentrated hydrochloric acid. N-functionalised derivatives of 5 and 6 are formed through alkylation, sulfonylation or acylation. Thus, consecutive treatments with methyl triflate and base gives the corresponding trimethylammonium-substituted iridabenzofurans while sulfonamide derivatives are formed with p-toluenesulfonyl chloride. N-Acylation of 5 or 6 with acid chlorides, however, selectively form either amide or imide products depending on the charge on the metal and the steric size of the acid chloride. Cationic 5 gives amide substituted products regardless of the conditions whereas neutral 6 rapidly undergoes di-N-acylation with excess benzoyl chloride under mild conditions to give the imide-substituted product Ir(C H O{N[C(O)Ph] -2}{OMe-7})Cl(PPh ) (13). Selective mono-acylation of 6 can be achieved with one equivalent of benzoyl chloride or with excess of the sterically congested pivaloyl chloride.

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Section: Resultsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Syntheses of Amino‐Substituted Iridabenzofurans and Subsequent Selective N‐Functionalisation

Frogley

Perera

Wright

2017

Chemistry A European J

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“…For example, monocyclic metallafurans can conveniently be prepared by insertion of alkyne into metal–acyl complexes, or insertion of alkynone, alkynoate, allenoate, and alkynol into complexes with metal‐hydride or metal‐carbon double/triple‐bonded functionalities . Metallabenzofurans, the most common fused‐ring metallafurans, can be prepared from the usage of polyfunctional alkynes or post‐modification of monocyclic metallafurans . Metallafurans are in general air‐ and moisture‐stable, and reactivities found are mostly related to the fused metallabenzene ring instead of the metallafuran ring itself .…”

Section: Methodsmentioning

confidence: 99%

“…Metallabenzofurans, the most common fused‐ring metallafurans, can be prepared from the usage of polyfunctional alkynes or post‐modification of monocyclic metallafurans . Metallafurans are in general air‐ and moisture‐stable, and reactivities found are mostly related to the fused metallabenzene ring instead of the metallafuran ring itself . Aromaticity of metallafurans is of fundamental importance and has been investigated by both experimental techniques (NMR) and theoretical calculations .…”

Section: Methodsmentioning

confidence: 99%

Phosphonium‐Ring‐Fused Bicyclic Metallafuran Complexes of Ruthenium and Osmium

Yeung

Chung

et al. 2019

Chemistry A European J

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Metallafuran complexes with a fused five‐membered phosphonium ring were synthesized from reactions between terminal ynones HC≡C(C=O)R and cis‐[Ru/Os(dppm)2Cl2] (dppm=1,1‐bis(diphenylphosphino)methane). A metal–vinylidene‐involving pathway was found to be an energetically feasible formation mechanism for these complexes. These phosphonium‐containing metallafurans, like many phosphonium‐functionalized drugs, have the ability to induce mitochondrial dysfunction. They also exhibit stronger cytotoxicity against several human cancer cell lines in comparison with their metal precursors and the classic anticancer drug cisplatin. Overall, this work provides structural and mechanistic insights for the rational design of functional metallacycles via activation of alkynes by RuII and OsII centers.

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“…Because of the synergistic interplay of theoretical and experimental investigations, numerous metallaaromatic molecules with interesting structural features and properties have been demonstrated over the past several decades. [3][4][5][6][7][8][9] According to the category of classical organic aromatics, metallaaromatics can be classified as those in which a metal fragment replaces the carbon atom in the framework of aromatic hydrocarbons and those that contain main-group heteroatoms. Representative examples of the former type are well known, such as metallabenzene, [10][11][12][13][14][15][16][17][18] metallabenzyne, [19][20][21][22][23] metallanaphthalene, [24][25][26] and metallaanthra-cene.…”

Section: Introductionmentioning

confidence: 99%

Metallaaromatics Containing Main‐group Heteroatoms

2017

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Metallaaromatics are metallacycles that are derived from the formal replacement of a carbon atom in the framework of organic aromatics with a metal fragment. As an important subclass of metallaaromatics, metallaaromatics that contain main‐group heteroatoms have attracted considerable attention. In the past ten years, we have developed several new methods to construct metallaaromatics as well as those containing main‐group heteroatoms, such as metallapyridine, metallapyridinium, metallapyridyne, metallafuran, metallabenzothiazole, metallabenzoxazole, metallabenzthiophene, aza‐metallapentalene and some novel tricyclic/tetracyclic metallaaromatics. In addition, interesting reactions such as the first hetero‐Diels Alder reaction between 1‐metalla‐1,3‐dienes and nitriles, the first intramolecular nucleophilic aromatic substitution (SNAr) reaction of metallabenzene, and the first iodine‐mediated electrophilic cyclizations of a metallabenzene complex were demonstrated. In this account, recent and novel approaches for their synthesis and property analyses are summarized. The structural diversity and unique properties of metallaaromatics containing main‐group heteroatoms will strongly inspire further investigation of these species and provide a wide range of potential applications.

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Fused-ring metallabenzenes

Cited by 143 publications

References 38 publications

Syntheses of Amino‐Substituted Iridabenzofurans and Subsequent Selective N‐Functionalisation

Syntheses of Amino‐Substituted Iridabenzofurans and Subsequent Selective N‐Functionalisation

Phosphonium‐Ring‐Fused Bicyclic Metallafuran Complexes of Ruthenium and Osmium

Metallaaromatics Containing Main‐group Heteroatoms

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