Synthesis and Characterization of Cyclopropaosmanaphthalenes Containing a Fused σ‐Aromatic Metallacyclopropene Unit

Chu, Zhenwei; He, Guomei; Cheng, Xiaoli; Deng, Zhirong; Chen, Jiangxi

doi:10.1002/anie.201904815

Cited by 31 publications

(21 citation statements)

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“…The authors proposed that the alkyne-coordinated osmium vinyl complexes are key intermediates, which could be protonated to give the final products (Scheme ). Complexes 51 and 52 are the first cyclopropametallanaphthalenes, and AICD analysis suggests they exhibit σ aromaticity for the cyclopropane ring and π aromaticity for the naphthalene ring …”

Section: Synthetic Methodsmentioning

confidence: 99%

“…It is interesting that, in the conversion of 48 to 50, three C(sp 3 )−H bonds are activated. 142 Oxidation of osmacyclohexa-1,4-dienes is another method with which to synthesize osmabenzenes. By using DDQ (dichloro-5,6-dicyano-1,4-benzoquinone) or CuCl 2 as the oxidant, Wright et al found that complexes 53 and 54 could be converted to 55 and 56, respectively (Scheme 20).…”

Section: Synthesis Of Metallabenzenesmentioning

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: Synthetic Methodsmentioning

confidence: 99%

Section: Synthesis Of Metallabenzenesmentioning

confidence: 99%

Metallaaromatic Chemistry: History and Development

2020

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“…[14] In addition, more organometallic complexes with σ-aromaticity were reported. [15] It's worth noting that σ-aromaticity can be dominant in a completely unsaturated three-membered ring (C-Os in Figure 2), which is traditionally dominated by πaromaticity. [16] However, those previous studies were only limited to the singlet state.…”

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confidence: 99%

Adaptive σ‐Aromaticity in an Unsaturated Three‐Membered Ring

Huang

Dai

Zhu

2020

Chemistry An Asian Journal

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Based on Hückel's and Baird's rules, species are aromatic either in the lowest singlet state (S 0) or the lowest triplet state (T 1) only. Thus, species with adaptive aromaticity (with aromaticity in both the S 0 and T 1 states) is particularly rare. On the other hand, σ-aromaticity in the T 1 state has been underdeveloped, let alone adaptive σ-aromaticity. Herein, via various aromaticity indices including NICS, ACID and EDDB, we demonstrate adaptive σ-aromaticity in an unsaturated three-membered ring, which is a traditional area [a

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“…Osmanaphthalene was synthesized by Chu et al in 2019. In that work, they reported the possible aromatic behavior of osmanaphthalene based on structural parameters (planarity and bond lengths) and typical 1 H NMR shifts for aromatic compounds …”

Section: Introductionmentioning

confidence: 99%

In Silico Analysis of the Electronic Delocalization in Some Double Fused-Ring Metallabenzenes

et al. 2021

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In the current work, some metallabenzenes with one and several fused rings were analyzed in terms of their electronic delocalization. These fused-ring metallabenzenes are known as metallabenzenoids, and their aromatic character is not free of controversy. The systems of the current work were designed from crystallographic data of some synthesized molecules, and their electronic delocalization (aromaticity) was computationally examined in terms of the molecular orbital analysis (Hückel’s rule), the induced magnetic field, and ring currents. The computational evidence allows us to understand if these molecules are or are not aromatic compounds.

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Synthesis and Characterization of Cyclopropaosmanaphthalenes Containing a Fused σ‐Aromatic Metallacyclopropene Unit

Cited by 31 publications

References 135 publications

Metallaaromatic Chemistry: History and Development

Metallaaromatic Chemistry: History and Development

Adaptive σ‐Aromaticity in an Unsaturated Three‐Membered Ring

In Silico Analysis of the Electronic Delocalization in Some Double Fused-Ring Metallabenzenes

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