Aromatic Dicupra[10]annulenes

Wei, Junnian; Zhang, Yongliang; Chi, Yue; Liu, Liang; Zhang, Wen‐Xiong; Xi, Zhenfeng

doi:10.1021/jacs.5b11317

Cited by 80 publications

(86 citation statements)

References 57 publications

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“…[217] Relatedt en-p-electron,a romatic dicupra [10]annulenes also have been recently reported. [218] Finally,i ts hould be noted that theoretical studies have suggesteds ome metallacyclobutadienes can also be aromatic. [100,[219][220][221] Scheme21.…”

Section: Metalla-analogues Of Classical Antiaromatic Compoundsmentioning

confidence: 99%

Recent Advances in Metallaaromatic Chemistry

Frogley

Wright

2017

Chemistry A European J

145

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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: Metalla-analogues Of Classical Antiaromatic Compoundsmentioning

confidence: 99%

Recent Advances in Metallaaromatic Chemistry

Frogley

Wright

2017

Chemistry A European J

145

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“…Compared with the chemistry of annulenes and dehydroannulenes, that of metalla‐analogs is much less developed. Reported metallaannulenes or metalladehydroannulenes are mainly small‐ring metallacycles, such as metallacyclobutadienes ( 1 ),, metallabenzenes ( 2 ), dimetallabenzenes ( 3 ), metallabenzynes ( 4 ),, metallacyclooctatetrenes and ten‐membered‐ring dimetallaannulenes ( 5 ),– despite the fact that many polycyclic metalla‐aromatics ( 6 ‐ 11 ) or spiro‐aromatic metallacycles ( 12 ) have been reported.…”

Section: Introductionmentioning

confidence: 99%

Synthesis, Characterization and Electronic Structure of Dirhenadehyro[12]annulene Complexes

et al. 2018

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Treatment of the SiMe3‐protected dichloro‐rhenium carbyne complexes Re{≡CCH=C(R)C≡CSiMe3}Cl2(PMe2Ph)3 (R = CMe3, 1‐adamantyl) with CsF in methanol directly afforded the 12‐membered metallacycles {ReCl(PMe2Ph)3}2{≡CCH=C(R)C≡C−}2. The electronic structure of the metallacycle was investigated by density functional calculations. The UV‐vis spectrum of the metallacycle shows a red‐shifted band compared to that of the starting dichlorocarbyne complex. Treatment of {ReCl(PMe2Ph)3}2{≡CCH=C(CMe3)C≡C−}2 with HCl produced the dichloro‐rhenium carbyne complex Re{≡CCH=C(CMe3)C≡CH}Cl2(PMe2Ph)3, which is consistent with the electronic structure of the 12‐membered metallacycles.

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“…[23] Aromaticity is recovered when the 10-MR is forced to be almost planar,a si n1 ,6-methano [10]annulene [24] [the NICS(0) value calculated in the centero fo ne of the two 6-MRs is À14.8 ppm, and that in the centero ft he large1 0-MR is À26.8 ppm].S imilarly,i nar ecent work, Xi and co-workers reported that as eries of synthesized dicupra [10]annulenes, which do not have the H···H stericr epulsion present in trans,cis,trans,cis,cis-cyclodecapentaene, are almostplanar and aromatic. [25] To further confirm the aromaticity of trans,cis,trans,cis,cis-cyclodecapentaene, we performed thef ollowing Gedankenexperiment. We removed these two out-of-plane hydrogen atoms and built the singlet biradical C 10 H 8 .G eometry optimization of this structure leads to closed-shelln aphthalene, whichi sc learly aromatic [NICS(0) = À8.5 ppm in the center of one of the 6-MRs].F or comparison, the same biradical was analyzed in its triplet state, Figure 4).…”

Section: Resultsmentioning

confidence: 99%

Hückel's Rule of Aromaticity Categorizes Aromatic closo Boron Hydride Clusters

Poater

Solà

Viñas

et al. 2016

Chemistry A European J

109

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Abstract:A direct connection is established between tridimensional aromatic closo boron hydride clusters and planar aromatic [n]annulenes for medium and large size boron clusters. In particular, our results prove the existence of a link between the two-dimensional Hückel rule followed by aromatic [n]-annulenes and Wade-Mingos' rule of three-dimensional aromaticity applied to the aromatic [BnHn] 2-closo boron hydride clusters. Our results show that closo boron hydride clusters can be categorized into different series according to the n value of the Hückel (4n+2) rule. The distinct categories studied in this work correspond to values of n = 1, 2, and 3. Each category increases in geometrical difficulty but, more importantly, it is possible to associate each category with the number of pentagonal layers in the structure perpendicular to the main axis. Category 1 has one pentagonal layer, category 2 has two, and category 3 has three.

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Aromatic Dicupra[10]annulenes

Cited by 80 publications

References 57 publications

Recent Advances in Metallaaromatic Chemistry

Recent Advances in Metallaaromatic Chemistry

Synthesis, Characterization and Electronic Structure of Dirhenadehyro[12]annulene Complexes

Hückel's Rule of Aromaticity Categorizes Aromatic closo Boron Hydride Clusters

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