Formation of the first organometallic catenane

Gruter, Gert Jan M.; Kanter, Frans J. J. de; Markies, Peter R.; Nomoto, Tateo; Akkerman, Otto S.; Bickelhaupt, F.

doi:10.1021/ja00078a072

Cited by 60 publications

(33 citation statements)

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“…This is reminiscent of analogous behavior of aryl protons inside the cavity of small metacyclophanes; [20,21] it has been ascribed to the van der Waals effect caused by steric congestion. [22] As similar changes have also been observed for 6 [9] and 7, [11] these phenomena are indicative of the rotaxane-type threading of a diarylmagnesium into a m-xylylene crown ether cavity. In view of the 1:2 ratio of the two components, three structures are conceivable: the double side-on complex 9a, the sideon/rotaxane complex 9b, and the double rotaxane complex 9c (Scheme 3).…”

Section: Complexation Of 8 With Diarylmagnesium Compoundssupporting

confidence: 77%

“…Two other pairs of shifts at δ ϭ 4.47 and 7.74 ppm and δ ϭ 4.20 and 8.60 ppm have equal intensities which is in line with 9b; this is further supported by the observation that the shifts of the first pair correspond to those of 9a indicating side-on coordination, while those for the second pair are typical for a rotaxane structure. [9,11] The least certain assignment is that of the pair at δ ϭ 4.09 and 8.56 ppm due to the low intensity; it cannot be excluded that these signals are caused by impurities, but on the other hand, the 4:1 ratio and the typical ''rotaxane shift range'' support the tentative assignment to 9c.…”

Section: Complexation Of 8 With Diarylmagnesium Compoundsmentioning

confidence: 99%

“…[1,2] An illustration is the high organolithium-like reactivity demonstrated by intra-annular metalation of 1 to 2 (Scheme 1), [3] by metalϪhalogen exchange as in 3 to furnish 4, [3,4] and by several ether cleavage reactions of substrates which are normally inert toward organomagnesium reagents. [2,5,6] Another challenging aspect is the formation of organometallic rotaxanes [7,8] such as 6, [1,2,9,10] and even catenanes 7 [11] from 5 (Scheme 2). They are of interest not negative entropy.…”

Section: Introductionmentioning

confidence: 99%

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In Quest of the Double Rotaxane Formation of the Bis(coronand) (1,5),(2,4)‐Durenetetrayl‐bis(18‐crown‐5) with Organomagnesium Compounds

et al. 2003

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The interaction between the title compound, bis(coronand) 8, and the diarylmagnesium compounds Ph 2 Mg and (ptBuC 6 H 4 ) 2 Mg in diethyl ether leads to the formation of 1:2 complexes (9 and 10, respectively), irrespective of the initial ratio of the components. In [D 8 ]toluene, the three complex types can be discerned by 1 H NMR spectroscopy: double side-on (9a, 10a), side-on/rotaxane (9b, 10b), and, to a very minor extent, double rotaxane (9c, 10c). In the case of 10a and 10b, the temperature dependence showed that rotaxane formation is enthalpically favored at the expense of a more

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Section: Complexation Of 8 With Diarylmagnesium Compoundssupporting

confidence: 77%

Section: Complexation Of 8 With Diarylmagnesium Compoundsmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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In Quest of the Double Rotaxane Formation of the Bis(coronand) (1,5),(2,4)‐Durenetetrayl‐bis(18‐crown‐5) with Organomagnesium Compounds

et al. 2003

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“…'H NMR (CDCI,): 79 (t,4H;CH,CN),3.13 (m,8 H ;SCH,),3.67 (s,4H;OCH,CH,O). 3.75 (t,4 H ;SCH,CH,O); MS (EI): m/z (%): 616 (100) [MIt;C,,H,,N,O,S,,(617.0): calcd C 35.04,H 3.27,N 4.54;found C 35.13,H 3.26,N 4. The green residue was extracted with CH,CI, (100 mL). The organic solution, after workup, gave 0.21 g (85 %)of unreacted 3.…”

Section: 5-bis(2-(2-(2-iodoethoxy)ethoxy)ethoxy)naphthalene (4 C)mentioning

confidence: 99%

Self‐assembling Tetrathiafulvalene‐based Rotaxanes and Catenanes

Li¹,

Stein²,

Becher³

et al. 1996

Chemistry A European J

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Abstract:A general stepwise approach is described for the preparation of tetrathiafulvalene (TTF)-based linear and monoand dimacrocyclic compounds incorporating one or two 1,4-dioxyphenylene, 9,10-dioxyanthrylene, or 1 3 -or 2,6-dioxy- [3]pseudocatenanes (i.e., both the cis and trans catenanes), in which the TTF units were clamped by the tetracationic macrocycle, isomerizations were completely prevented even in the presence of trifluoroacetic acid. All new rotaxanes and catenanes were characterized by electrospray mass spectrometry, and the cis-and trans-[3]pseudocatenanes were additionally investigated by 'H NMR spectroscopy. The electrochemical and spectral properties of the rotaxane and the catenanes are reported. Catenane formation increases the redox potentials of the TTF unit. The results demonstrate the versatility of TTF as a building block in the construction of supramolecular structures.

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“…[188] Die Gruppe von Bickelhaupt stellte außerdem ein Organomagnesium [2]catenan [189] 148-Mg II und ein bicyclisches [3]Rotaxan her. [190] [191] Wisner beschrieb die Bildung von [2]Rotaxanen (z.…”

Section: Metallionen-koordination Innerhalb Der Achseunclassified

Strategien und Taktiken für die metallgesteuerte Synthese von Rotaxanen, Knoten, Catenanen und Verschlingungen höherer Ordnung

et al. 2011

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Mehr als ein Vierteljahrhundert nach der ersten Metalltemplatsynthese eines [2]Catenans in Straßburg existiert nun eine Fülle an Strategien zum Aufbau mechanisch verbundener und verflochtener Strukturen auf molekularer Ebene. Catenane, Rotaxane, Knoten und Borromäische Ringe sind alle erfolgreich über Methoden zugänglich, in denen Metallionen eine Schlüsselrolle spielen. Ursprünglich wurden Metallionen ausschließlich aufgrund ihrer Koordinationschemie verwendet, indem sie entweder die einzelnen Bausteine auf eine Weise anordneten, die durch anschließende Reaktionen die Erzeugung der verschlungenen Produkte ermöglichte, oder indem sie selbst als wesentlicher Bestandteil der Ringe oder als “Stopper” dienten. Vor kurzem wurde die Rolle des Metalls auch auf die Katalyse ausgedehnt: Die Metallionen ordnen die Bausteine nicht nur zu einer verflochtenen oder eingefädelten Struktur an, sondern fördern auch aktiv die Strukturbildung durch kovalenten Einfangen. Dieser Aufsatz fasst die Strategien zur Bildung mechanisch verbundener Molekülstrukturen mit Metallionen zusammen und diskutiert die Taktiken, die zum Aufbau von Überkreuzungen, zur Maximierung der Ausbeuten verschlungener und nichtverschlungener Produkte und zur Bildung eingefädelter oder verflochtener Intermediate durch kovalenten Einfang zur Verfügung stehen.

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Formation of the first organometallic catenane

Cited by 60 publications

References 0 publications

In Quest of the Double Rotaxane Formation of the Bis(coronand) (1,5),(2,4)‐Durenetetrayl‐bis(18‐crown‐5) with Organomagnesium Compounds

In Quest of the Double Rotaxane Formation of the Bis(coronand) (1,5),(2,4)‐Durenetetrayl‐bis(18‐crown‐5) with Organomagnesium Compounds

Self‐assembling Tetrathiafulvalene‐based Rotaxanes and Catenanes

Strategien und Taktiken für die metallgesteuerte Synthese von Rotaxanen, Knoten, Catenanen und Verschlingungen höherer Ordnung

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