Synthesis of Aromatic Aza-metallapentalenes from Metallabenzene via Sequential Ring Contraction/Annulation

Wang, Tongdao; Han, Feifei; Huang, Haiping; Li, Jinhua; Zhang, Hong; Zhu, Jun; Lin, Zhenyang; Xia, Haiping

doi:10.1038/srep09584

Cited by 20 publications

(15 citation statements)

References 41 publications

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“…The previously reported aza‐osmapentalene was synthesized by reaction of osmacyclopentadiene derivative 1 a with propynol as the new carbon source. To extend the strategy, we envisioned that heterocumulenes may be an appropriate candidate for introducing new heteroatoms into the metallacycles.…”

Section: Resultsmentioning

confidence: 99%

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Access to Metal‐Bridged Osmathiazine Derivatives by a Formal [4+2] Cyclization

Lin

Zhang

et al. 2019

Chemistry A European J

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Treatmento fo smacyclopentadiene derivatives 1 with phenyl or isopropyl isothiocyanate gave the fused five and six-membered osmacycles 2-5 by aformal [4+ +2] cyclization. The facile protonation of the newly generated exocyclic imine in complexes 2-5 afforded conjugation-extended osmacycle derivatives 6-9.C ompounds 2-9 each contain two main-group heteroatoms (N and S) in the fused six-membered ring located at the ortho (for S) and para (for N) positions relative to the osmiumc entre;t hese speciesc an be re-garded as rare osma-1,3-thiazine derivatives and represent the first fused metallathiazine derivatives. In contrast to the non-planar organic 6H-1,3-thiazine, nearly coplanar metallathiazines 8 and 9 can be achievedb yt uning the groups on the two nitrogen atoms. These unique metal-bridged osma-1,3-thiazine derivatives exhibit remarkable stabilities, broad spectrala bsorptions spanning the visible spectra, andc onsiderable photothermal properties, which suggests their potential applications in materialscience.Scheme1.The skeleton structures of metallapentalene (I), aza-metallapentalene (II) and metallathiazinederivatives (III).[a] J.

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Section: Resultsmentioning

confidence: 99%

“…Based on the unique structure of metallapentalene (Scheme , type I ), we have recently reported an aza‐metallapentalene (Scheme , type II ), in which a carbon atom was replaced by a nitrogen atom . In this respect, we are interested to investigate whether more main‐group heteroatoms can be embedded in this system.…”

Section: Introductionmentioning

confidence: 99%

Access to Metal‐Bridged Osmathiazine Derivatives by a Formal [4+2] Cyclization

Lin

Zhang

et al. 2019

Chemistry A European J

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“…26 In addition, the first aza-metallapentalene was also synthesized. 29 The treatment of osmabenzene 9 with aniline led to the formation of osmapentafulvene 10 in high isolated yield (Scheme 10). Refluxing 10 with phenylpropynol in the presence of Ag 2 O and trimethylamine, yielded the metallabicyclic product 11, which could easily convert to the azaosmapentalene 12.…”

Section: C Framework: Metallapentalenementioning

confidence: 99%

Carbolong Chemistry: A Story of Carbon Chain Ligands and Transition Metals

2018

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The construction of metal-carbon bonds is one of the most important issues of organometallic chemistry. However, the chelation of polydentate ligands to a metal via several metal-carbon bonds is rare. Metallapentalyne, which can be viewed as a 7-carbon (7C) chain coordinated to a metal via three metal-carbon bonds, was first reported in 2013. Although metallapentalyne contains a metal-carbon triple bond in a five-membered ring (5MR) and the bond angle around the carbyne carbon is only 129.5°, metallapentalyne exhibits excellent stability to air, moisture, and heat. Metallapentalyne possesses the rare planar Möbius aromaticity, which is in sharp contrast to the Hückel antiaromaticity in pentalyne. The metal fragment not only relieves the large ring strain present in pentalyne but also results in the transformation of the antiaromaticity in pentalyne to aromaticity in metallapentalyne. With the extension of the carbon chain from 7 to 12 carbon atoms, a series of novel polycyclic frameworks were constructed via the formation of several metal-carbon bonds. Some interesting phenomena were observed for these complexes. For instance, (1) the carbyne carbon of the 7C framework could react with both nucleophilic and electrophilic reagents, leading to the formation of 16- and 18-electron metallapentalenes; (2) σ aromaticity was first observed in an unsaturated system in the 8C framework; (3) two classical antiaromatic frameworks, cyclobutadiene and pentalene, were simultaneously stabilized in the 9C framework for the first time; (4) three fused 5MRs bridged by a metal are coplanar in the 10C framework; (5) the first [2 + 2 + 2] cycloaddition of a late transition metal carbyne complex with alkynes was realized during the construction of an 11C framework; (6) the largest number of carbon atoms coordinated to a metal atom in the equatorial plane was observed in the 12C framework; and (7) sharing of the transition metal by multiple aromatic units has seldom been observed in the metalla-aromatics. Therefore, the term carbolong chemistry has been used to describe the chemistry of these novel frameworks. More interestingly, carbolong complexes exhibit diverse properties, which could lead to potential future applications. As the discovery and creation of molecular fragments lead to advancements in chemistry, medical science, and materials chemistry, these novel polydentate carbon chain chelates might have important influences in these fields due to their facile synthesis, high stability, and unique properties.

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“…Loss of the hydroxyl group then gives the aza‐osmapentalene 69 . Unlike azapentalene, the aza‐metallapentalenes are highly stable, planar, aromatic species …”

Section: Metalla‐analogues Of Classical Antiaromatic Compoundsmentioning

confidence: 99%

“…However, this is not the case for all metallaaromatics and recent landmark studies have uncovered important exceptions. Within the last few years aromatic, highly stable metallapentalenes and metallapentalynes have been reported and these are the metalla‐analogues of the anti‐aromatic organic compounds pentalene and pentalyne . Furthermore, the first spiro‐metallaaromatics have now been isolated, and these have no organic analogues.…”

Section: Introductionmentioning

confidence: 99%

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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Synthesis of Aromatic Aza-metallapentalenes from Metallabenzene via Sequential Ring Contraction/Annulation

Cited by 20 publications

References 41 publications

Access to Metal‐Bridged Osmathiazine Derivatives by a Formal [4+2] Cyclization

Access to Metal‐Bridged Osmathiazine Derivatives by a Formal [4+2] Cyclization

Carbolong Chemistry: A Story of Carbon Chain Ligands and Transition Metals

Recent Advances in Metallaaromatic Chemistry

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