Synthesis and Characterization of a Rhenabenzyne Complex

Chen, Jiangxi; Sung, Ho Yeung; Williams, Ian D.; Lin, Zhenyang; Jia, Guochen

doi:10.1002/anie.201104587

Cited by 77 publications

(33 citation statements)

References 85 publications

(22 reference statements)

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“…The mechanism for the formation of isoosmabenzene 2 is a formal [3+3] cycloaddition that has been discussed previously 10a. Once 2 has been generated, its ethoxyl group on C3 extracts a proton (presumably from trace amounts of acids in chloroform or from the eliminated ethanol) to form an onium salt A , which undergoes ethanol elimination to generate 3′ , a resonance form of 3 9a. d, g…”

Section: Resultsmentioning

confidence: 99%

Conversions of Osmabenzyne and Isoosmabenzene

Zhao

Zhu

Huang

et al. 2012

Chemistry A European J

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We report herein the first example of the conversion of metallabenzyne II and isometallabenzene III. The osmium hydride vinylidene complex 1 reacts with HC≡CCH(OEt)(2) to give osmabenzyne 3 via isoosmabenzene 2. Compound 3 exhibits high thermal stability in air. Nonetheless, nucleophilic attack at 3 provides isoosmabenzenes 4 a and 4 b, or opens the ring to produce 5 a and 5 b. We propose mechanisms to disclose the intrinsic connection between the six-membered metallacycles, and carry out DFT calculations to rationalize the regioselectivity of the nucleophilic addition reactions.

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Section: Resultsmentioning

confidence: 99%

Conversions of Osmabenzyne and Isoosmabenzene

Zhao

Zhu

Huang

et al. 2012

Chemistry A European J

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“…[148] Rhenabenzynes have been prepared by thermalr earrangement of ethynylvinylcarbyne complexes. [143,149] Interestingly,i fthel igands are modified in this last method, dirhenadehydro [12]annulenes are formed. [150] Several fused-ring derivatives of metallabenzynes are also known.T wo osmanaphthalynes have been prepared from vinylcarbyne precursors, by either Zn reduction [151] or CH activation, [118] and an osmabenzyne with af used thiophene ring has been prepared by CH activation of av inylcarbeneligand.…”

Section: Metallabenzynesmentioning

confidence: 99%

Recent Advances in Metallaaromatic Chemistry

Frogley

Wright

2017

Chemistry A European J

142

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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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“…卡拜化合物 [24] . 最近, 夏海平等 [25] 目前只有 3 个铼苯炔化合物被成功合成出来 [26,27] , [28] 可以发生硝化反应生成化合物 60, Ir{C 5 H 4 (SMe)}Cl 2 (PPh 3 ) 2 (61) [29] 可以发生溴化反应生成化合物 62 (Scheme 8).…”

Section: Methodsunclassified

Synthesis and Chemical Properties of Metallabenzynes

Chen¹,

He²,

Jia³

2013

Chin. J. Org. Chem.

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Metallabenzynes are an interesting class of metallaraomatics. They can be regarded as transition-metal analogs of benzyne in which a C atom is replaced by an isolobal transition metal fragment. The chemistry of this class of compounds has received much recent attention. A series of metallabenzynes containing osmium and rhenium have been isolated. It has also been demonstrated both experimentally and theoretically that metallabenzynes can have properties of both aromatic organic compounds and organometallic compounds. For example, metallabenzynes, like organic aromatic compounds, could undergo electrophilic substitution reactions to give new metallabenzynes; react with nucleophiles to generate metallabenzene species through addition of nucleophiles at the carbyne carbons of metallabenzynes and undergo reductive elimination to give carbene complexes.

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Synthesis and Characterization of a Rhenabenzyne Complex

Cited by 77 publications

References 85 publications

Conversions of Osmabenzyne and Isoosmabenzene

Conversions of Osmabenzyne and Isoosmabenzene

Recent Advances in Metallaaromatic Chemistry

Synthesis and Chemical Properties of Metallabenzynes

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