Synthesis and Properties of a Superphane with One Thiophene and One CpCo-Stabilized Cyclobutadiene Ring

Gath, Silke; Gleiter, Rolf; Schaller, Rolf J.; Röminger, Frank

doi:10.1021/om030619k

Cited by 11 publications

(7 citation statements)

References 22 publications

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“…After protection of the acidic proton in 25 by a cyano group, the stage was set to reduce the lower part of 26 by a phenylcopper reagent. This reaction afforded 27, which was transferred to the [10]cyclophenacene 28.…”

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confidence: 99%

From superphanes to beltenes

Gleiter

Hellbach

Gath

et al. 2006

Pure and Applied Chemistry

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This short review describes paths to superphanes with metal-stabilized cyclobutadiene and cyclopentadienone rings in a one-pot and stepwise fashion. The stepwise synthesis also led to a new class of belt-like systems with large rings composed of CpCo-stabilized cyclobutadiene rings connected with propane chains. Finally, our research yielded the first beltenes composed of alternating four-and eight-membered conjugated rings.A superphane is a phane in which all hydrogen atoms of the cyclic conjugated rings are tethered by bridges. This definition goes back to Boekelheide and Hopf [1]. So far, a number of superphanes with benzene rings, heterocycles, and metal-stabilized π-systems have been prepared [2]. Our affair with superphanes started with the reaction of cyclodeca-1,6-diyne 1 with CpCoL 2 , which afforded in a onepot reaction the superphane 2 (Scheme 1) [3]. This reaction was first extended to other cyclic alkynes such as cyclotetradeca-1,8-diyne [4] and cyclooctadeca-1,10-diyne [5]. The superphanes proved to be excellent starting materials for bridged cage hydrocarbons [6] and model compounds to study the interactions between two metal centers separated by chains of different lengths [7]. This encouraged us to design also a path for a stepwise synthesis of superphanes with four-and five-membered [8-10] rings as summarized in Scheme 2. The resulting superphanes are stable at room temperature, and their molecular structures were investigated. The intermediates 5-7, which were cyclized in an intramolecular reaction to 2 and 8-11, stimulated us to look for higher oligomers.

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confidence: 99%

From superphanes to beltenes

Gleiter

Hellbach

Gath

et al. 2006

Pure and Applied Chemistry

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“…In Figures and we show as an example the molecular structures of 11 and 13 . The structure of 8 was previously reported . In the molecular structures of 8 − 12 the propandiyl bridges at the positions α to the sulfur atom adopt a conformation in which the central CH 2 groups of the chains point away from the heteroatom (see Figure ).…”

Section: Resultsmentioning

confidence: 91%

“…Syntheses. Our previous studies showed that the best way to synthesize 8 − 13 is by starting with the tricyclic diyne 19 …”

Section: Resultsmentioning

confidence: 99%

“…1,2,3,6,7,8,9,10,11,14,15,16-Dodecahydro-4,5,12,13-tetradehydro-1 H ,9 H -dicyclodeca[ b,d ] thiophene ( 19 ) and the superphane 8 were prepared according to literature methods. , …”

Section: Methodsmentioning

confidence: 99%

“…Such species can also be generated by discriminating the sides of the superphanes structurally as shown in 5 − 7 . − For studying the electronic interaction prevailing in a mixed superphane we developed a route to synthesize various derivatives of 7 . Recently, we reported briefly the synthesis of 8 , which can be looked at as a mixed superphane between 3 and 4 . In this paper we describe in detail the synthesis of the superphanes 8 − 13 and their structural and electrochemical properties.…”

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confidence: 99%

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Transannular Interactions in Mixed Superphanes with One Thiophene and One CpCo-Stabilized Cyclobutadiene Ring: Syntheses, Structures, and Electrochemistry

et al. 2007

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Superphanes consisting of one thiophene ring and various substituted RCo-stabilized cyclobutadiene (CBD) rings (R = Cp, C5H4(CH3), C5(CH3)5, C5H4(Si(CH3)3), C5H4(COCH3), 8−12) and one superphane with one thiophene ring and one CpCo-stabilized cyclopentadienone ring (13) were synthesized. The starting point was a tricyclic diyne with a central thiophene ring and two condensed 4-cyclodecynes, 19. Heating of 19 with RCo(COD) yielded 8−12, whereas the heating of 19 with CpCo(CO)2 gave 13. X-ray structural investigation of 8−13 afforded the geometrical parameters in the solid state. Cyclic voltammetry showed a strong interaction between the thiophene ring and the CpCo-stabilized cyclobutadiene part. This interaction was substantiated by comparison between the CV data of 8−12 and model systems containing only the CpCo(CBD) part.

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(1,5-Cyclooctadiene)(cyclopentadienyl)cobalt(I)

Pauson

Chelliah²

2007

Encyclopedia of Reagents for Organic Synthesis

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Synthesis and Properties of a Superphane with One Thiophene and One CpCo-Stabilized Cyclobutadiene Ring

Cited by 11 publications

References 22 publications

From superphanes to beltenes

From superphanes to beltenes

Transannular Interactions in Mixed Superphanes with One Thiophene and One CpCo-Stabilized Cyclobutadiene Ring: Syntheses, Structures, and Electrochemistry

(1,5-Cyclooctadiene)(cyclopentadienyl)cobalt(I)

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