Tunable haptotropic metal migration in fused arenes: towards organometallic switches

Dötz, Karl Heinz; Jahr, Holger C.

doi:10.1002/tcr.20007

Cited by 49 publications

(32 citation statements)

References 34 publications

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“…Up to three Ru(cyclopentadienyl) fragments were found to be η 6 ‐coordinated to alternating phenylenes in [6]CPP , and DFT calculations shed light on the observed regioselectivity. An interesting question that remains open is whether the organometallic complexes are fluxional in solution, that is, whether the metallic motives are “walking” along the rings, as has been demonstrated in related planar systems …”

Section: Metal Coordinationmentioning

confidence: 99%

The Supramolecular Chemistry of Strained Carbon Nanohoops

2019

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Since 1996, a growing number of strained macrocycles, comprising only sp2‐ or sp‐hybridized carbon atoms within the ring, have become synthetically accessible, with the [n]cycloparaphenyleneacetylenes (CPPAs) and the [n]cycloparaphenylenes (CPPs) being the most prominent examples. Now that robust and relatively general synthetic routes toward a diverse range of nanohoop structures have become available, the research focus is beginning to shift towards the exploration of their properties and applications. From a supramolecular chemistry perspective, these macrocycles offer unique opportunities as a result of their near‐perfect circular shape, the unusually high degree of shape‐persistence, and the presence of both convex and concave π‐faces. In this Minireview, we give an overview on the use of strained carbon‐rich nanohoops in host–guest chemistry, the preparation of mechanically interlocked architectures, and crystal engineering.

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Section: Metal Coordinationmentioning

confidence: 99%

The Supramolecular Chemistry of Strained Carbon Nanohoops

2019

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“…Dçtz and Jahr suggested that these haptotropic migrations can be used as novel organometallic molecular switches [72] in which this rearrangement can be tuned by modification of the reaction conditions or by photoinduction of these chemical species. They also reviewed a variety of benzannulation reactions where this haptotropic migration plays an important role in the synthesis and regioselectivity of organic compounds.…”

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confidence: 99%

Dötz Benzannulation Reactions: Heteroatom and Substituent Effects in Chromium Fischer Carbene Complexes

Jiménez-Halla

Solà

2009

Chemistry A European J

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We have carried out a theoretical investigation of the Dötz reaction between acetylene and a series of chromium Fischer-type carbenes [(CO)(5)Cr=C(X)R] with different representative substituents (R=CH=CH(2), Ph) and heteroatom ligands (X=OH, NH(2), OCH(3), N(CH(3))(2)) by using density functional theory with the B3LYP functional. We have studied the Dötz and chromahexatriene mechanisms of benzannulation and also the reaction mechanism leading to cyclopentannulation. For the benzannulation, it was found that the most likely mechanism in the case of vinylcarbenes is the chromahexatriene route, whereas for phenylcarbenes, the Dötz route via a ketene intermediate is clearly the most favorable. The reactions leading to the cyclopentannulated and benzannulated products are more exothermic with vinylcarbenes than with phenylcarbenes and also more exothermic with alkoxycarbenes than with aminocarbenes. The relative stability of the cyclopentannulated products as compared with the benzannulated products increases for bulkier X substituents and on going from alkoxy- to aminocarbenes. The kinetic data concurs with the experimental product distribution found for vinylcarbenes, by which mainly benzannulated products are obtained, and dimethylaminophenylcarbenes, which lead exclusively to cyclopentannulated adducts.

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“…Bis zu drei Ru(cyclopentadienyl)‐Fragmente mit η 6 ‐Koordination wurden auf alternierenden Phenylenen im [6]CPP gefunden, und ihre Regioselektivität wurde mittels DFT‐Rechnungen aufgeklärt. Eine interessante, aber offene Frage bleibt, ob die metallorganischen Komplexe in Lösung beweglich sind, d. h., ob die metallischen Bausteine entlang der Ringe wandern, wie es in verwandten Planarsystemen gezeigt wurde …”

Section: Koordination An Metalleunclassified

Supramolekulare Chemie von gespannten Kohlenstoffnanoreifen

Delius

2019

Angewandte Chemie

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Seit 1996 ist eine stetig wachsende Anzahl von hoch gespannten Makrozyklen präparativ zugänglich geworden, die lediglich sp2‐ oder sp‐hybridisierte Kohlenstoffatome im Ring enthalten, wobei [n]Cycloparaphenylenacetylene (CPPAs) und [n]Cycloparaphenylene (CPPs) die wichtigsten Beispiele dieser Klasse darstellen. Nachdem nun robuste und relativ allgemeine Synthesewege zu einer Vielzahl von Nanoreifen‐Strukturen zur Verfügung stehen, beginnt sich der Forschungsschwerpunkt auf die Erforschung ihrer Eigenschaften und Anwendungen zu verlagern. Aus Sicht der supramolekularen Chemie bieten diese Makrozyklen wegen ihrer nahezu perfekten Kreisform, der ungewöhnlich hohen Formstabilität und der Gegenwart von konvexen und konkaven π‐Flächen einzigartige Möglichkeiten. In diesem Kurzaufsatz besprechen wir den Einsatz von gespannten kohlenstoffreichen Nanoreifen in der Wirt‐Gast‐Chemie, der Herstellung von mechanisch verzahnten Architekturen und dem definierten Kristalldesign.

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Tunable haptotropic metal migration in fused arenes: towards organometallic switches

Cited by 49 publications

References 34 publications

The Supramolecular Chemistry of Strained Carbon Nanohoops

The Supramolecular Chemistry of Strained Carbon Nanohoops

Dötz Benzannulation Reactions: Heteroatom and Substituent Effects in Chromium Fischer Carbene Complexes

Supramolekulare Chemie von gespannten Kohlenstoffnanoreifen

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