Metallapentalenofuran: Shifting Metallafuran Rings Promoted by Substituent Effects

Hua, Yuhui; Lan, Qing; Fei, Jiawei; Tang, Chun; Lin, Jie; Zha, Hexukun; Chen, Shiyan; Lu, Yinghua; Chen, Jiangxi; He, Xumin; Xia, Haiping

doi:10.1002/chem.201802928

Cited by 12 publications

(4 citation statements)

References 123 publications

(53 reference statements)

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“…545 Electrophilic attack at the carbonyl group in 811 afforded another CCCN-type complex 812, and interestingly, this complex can be viewed as an osmapentalene derivative fused with a pyridine. Addition of HClO 4 reversibly protonated the nitrogen atom in the osmapyridine ring, and the pendant 546 It is obvious that the metallafuran ring shifted from right to left during the process from 815 to 816. DFT calculations suggest the intrinsic factor for this shift is mainly the steric effect on different rings.…”

Section: Reactivities Of Dianion Metallolesmentioning

confidence: 99%

“…Further treatment with t- BuOK and H 2 O eliminated the phosphonium group attached in the osmapentalenofuran cycle, generating 816 (Scheme ). It is obvious that the metallafuran ring shifted from right to left during the process from 815 to 816 . DFT calculations suggest the intrinsic factor for this shift is mainly the steric effect on different rings.…”

Section: Reactivity Studiesmentioning

confidence: 99%

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Metallaaromatic Chemistry: History and Development

2020

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Since the prediction of the existence of metallabenzenes in 1979, metallaaromatic chemistry has developed rapidly, due to its importance in both experimental and theoretical fields. Now six major types of metallaromatic compounds, metallabenzenes, metallabenzynes, heterometallaaromatics, dianion metalloles, metallapentalenes and metallapentalynes (also termed carbolongs), and spiro metalloles, have been reported and extensively studied. Their parent organic analogues may be aromatic, non-aromatic, or even anti-aromatic. These unique systems not only enrich the large family of aromatics, but they also broaden our understanding and extend the concept of aromaticity. This review provides a comprehensive overview of metallaaromatic chemistry. We have focused on not only the six major classes of metallaaromatics, including the main-group-metal-based metallaaromatics, but also other types, such as metallacyclobutadienes and metallacyclopropenes. The structures, synthetic methods, and reactivities are described, their applications are covered, and the challenges and future prospects of the area are discussed. The criteria commonly used to judge the aromaticity of metallaaromatics are presented.

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Section: Reactivities Of Dianion Metallolesmentioning

confidence: 99%

Section: Reactivity Studiesmentioning

confidence: 99%

Metallaaromatic Chemistry: History and Development

2020

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“…Recently, Xia and coworkers documented a series of five-membered cyclic metal carbyne complexes, i.e., osmapentalynes [47][48][49][50][51] and ruthenapentalynes [52]. The carbine-carbon bond angles in the metallapentalynes are around 130 • , which are much smaller than those of the acyclic metal carbynes (180 • ).…”

Section: Reactivity Of Five-membered Metallapentalynesmentioning

confidence: 99%

Recent Advances in the Reactions of Cyclic Carbynes

Qian¹,

Ding²,

Du³

et al. 2020

Molecules

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The acyclic organic alkynes and carbyne bonds exhibit linear shapes. Metallabenzynes and metallapentalynes are six- or five-membered metallacycles containing carbynes, whose carbine-carbon bond angles are less than 180°. Such distortion results in considerable ring strain, resulting in the unprecedented reactivity compared with acyclic carbynes. Meanwhile, the aromaticity of these metallacycles would stabilize the ring system. The fascinating combination of ring strain and aromaticity would lead to interesting reactivities. This mini review summarized recent findings on the reactivity of the metal–carbon triple bonds and the aromatic ring system. In the case of metallabenzynes, aromaticity would prevail over ring strain. The reactions are similar to those of organic aromatics, especially in electrophilic reactions. Meanwhile, fragmentation of metallacarbynes might be observed via migratory insertion if the aromaticity of metallacarbynes is strongly affected. In the case of metallapentalynes, the extremely small bond angle would result in high reactivity of the carbyne moiety, which would undergo typical reactions for organic alkynes, including interaction with coinage metal complexes, electrophilic reactions, nucleophilic reactions and cycloaddition reactions, whereas the strong aromaticity ensured the integrity of the bicyclic framework of metallapentalynes throughout all reported reaction conditions.

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“…[1][2][3][4][5] Over the years, the preparation and characterization of various metallabenzenes have been reported. [6][7][8][9][10][11][12][13] The aromaticity of metallabenzenes compared to benzene and cyclic heteroaromatics has been investigated. [14][15][16][17][18] As an example, replacing a CH of benzene with isolobal fragments of iridium leads to the synthesis of different iridabenzenes.…”

Section: Introductionmentioning

confidence: 99%

Substituent effects on the structure and properties of (para-C₅H₄X)Ir(PH₃)₃ complexes in the ground state (S₀) and first singlet excited state (S₁): DFT and TD-DFT investigations

Shalmani

Ghiasi

Marjani

2020

Journal of Chemical Research

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The ground and lowest singlet excited state geometries of selected ( para-C5H4X)Ir(PH3)3 iridabenzene complexes ( para-substituent = NH2, OMe, Me, H, F, Cl, CCl3, CF3, NO2) are optimized using the MPW1PW91 procedure employing the LanL2DZ(Ir) and 6-311G(d, p) (C, H, N, O, P, F, Cl, P) basis sets. The excited state is generated using the time-dependent density function method. The effects of electron-donating groups and electron-withdrawing groups on the energy, atomization energy, rotational constants, and frontier orbital energies in the first singlet excited state (S1) of iridabenzene are investigated and compared to those of the ground state (S0). The Ir–C and Ir–P bonds in the studied molecules are analyzed by electron localization function and localized-orbital locator methods. The correlations between the Ir-C and Ir–P bond distances, electron localization function, and localized-orbital locator values Hammett constants (σp) and dual parameters (σI and σR) are given for the two studied states. The para-delocalization index is used for investigation of the aromaticity of the studied complexes.

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Metallapentalenofuran: Shifting Metallafuran Rings Promoted by Substituent Effects

Cited by 12 publications

References 123 publications

Metallaaromatic Chemistry: History and Development

Metallaaromatic Chemistry: History and Development

Recent Advances in the Reactions of Cyclic Carbynes

Substituent effects on the structure and properties of (para-C₅H₄X)Ir(PH₃)₃ complexes in the ground state (S₀) and first singlet excited state (S₁): DFT and TD-DFT investigations

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Metallapentalenofuran: Shifting Metallafuran Rings Promoted by Substituent Effects

Cited by 12 publications

References 123 publications

Metallaaromatic Chemistry: History and Development

Metallaaromatic Chemistry: History and Development

Recent Advances in the Reactions of Cyclic Carbynes

Substituent effects on the structure and properties of (para-C5H4X)Ir(PH3)3 complexes in the ground state (S0) and first singlet excited state (S1): DFT and TD-DFT investigations

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Product

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Substituent effects on the structure and properties of (para-C₅H₄X)Ir(PH₃)₃ complexes in the ground state (S₀) and first singlet excited state (S₁): DFT and TD-DFT investigations