18‐, 20‐ und 22 gliedrige Dimetallaortho‐, ‐meta‐und ‐para[7.7]cyclophane ‐ die ersten typischen Metallaphane

Lindner, Ekkehard; Wassing, Walter; Fawzi, Riad; Steimann, Manfred

doi:10.1002/ange.19941060330

Cited by 9 publications

(4 citation statements)

References 16 publications

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“…The remainder was dissolved in 50 mL of dichloromethane, and the solution was filtered (P4), and then concentrated in vacuo. 3 J PC ϭ 6.5 Hz, meta-Ph), 120.5 (s, CH, bipy), 32.5-32.2 (m, CH 2 CH 2 CH 2 CH 2 PPh 2 and CH 2 CH 2 CH 2 CH 2 PPh 2 ) 28.0 (d, 1 J PC ϭ 11.5 Hz, CH 2 CH 2 CH 2 CH 2 PPh 2 ), 25.7 (d, 2 J PC ϭ 16.2 Hz, CH 2 CH 2 CH 2 CH 2 PPh 2 ). - 31 Tetrachlorodiplatinacyclophane 7c: Solutions of bis(benzonitrile)dichloroplatinum(II) (1.35 g, 2.858 mmol) and of 6c (1.82 g, 2.860 mmol) in 200 mL of dichloromethane each were simultaneously added dropwise within 2 h into 200 mL of dichloromethane.…”

Section: General Procedures For the Preparation Of The Diphosphanes 6a-cmentioning

confidence: 99%

“…[2] A couple of years later, the first synthesis of typical metallacyclophanes was published in the literature. [3] This kind of macrocycle presents the classically bridged cyclophane structure with aromatic units at the bottom and the top of the molecule, whereas the metals are located in the center of the aliphatic chain. [4] The introduction of transition metal fragments leads to a remarkable influence on the structure of the cyclophane framework.…”

Section: Introductionmentioning

confidence: 99%

“…[4] The introduction of transition metal fragments leads to a remarkable influence on the structure of the cyclophane framework. [3,5] Furthermore, a new potential reactive center is obtained, which can, for example, be used for the insertion of carbon monoxide into M-C σ bonds [3,5] or for catalysis. [6] Meanwhile several methods for the incorporation of transition metals into the cyclophane framework are known.…”

Section: Introductionmentioning

confidence: 99%

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Inclusion of Copper(I) into a Novel Bipyridine-Containing Tetraphosphadiplatinacyclophane

Lindner

Veigel

Ortner

et al. 2000

Eur. J. Inorg. Chem.

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The 5,5′‐bis(hydroxyalkyl)‐2,2′‐bipyridines 4a–c (Scheme 1) were prepared either in one step (4b, 4c) or in four steps (4a) starting with 5,5′‐dimethyl‐2,2′‐bipyridine in each case. Reaction of 4a–c with mesyl chloride afforded the bis(mesylates) [–C5H3N–(CH2)n–CH2–OSO2Me]2 5a–c [n = 1 (a), 2 (b), 3 (c)], which could easily be transformed into the diphosphanes 6a–c by reaction with LiPPh2. Treatment of 6c, 6b with Cl2Pt(NCPh)2 and (RC6H4)2Pt(COD) according to the high‐dilution method resulted in the formation of the tetraphosphadiplatinacyclophanes [–C5H3N–(CH2)4–PPh2PtCl2PPh2–(CH2)4–C5H3N–]2 (7c) and [–C5H3N–(CH2)3–PPh2Pt(C6H4R)2PPh2–(CH2)3–C5H3N–]2 (8b, 9b) (8b: R = H, 9b: R = tBu), respectively (Scheme 2). The molecular structures of 8b and 9b were elucidated by X‐ray structural analyses. The noncoordinated bipyridine moieties in 8b were employed to encapsulate copper(I) to give the host/guest complex 10b (Scheme 3), which was investigated by FAB‐MS, NMR spectroscopy, and cyclovoltammetry. 10b exhibited a quasi‐reversible oxidation at E1/2 = –0.31 V and an electrodeposition‐redissolution redox system at E1/2 = –0.79 V, owing to the formation of copper at the surface of the working electrode.

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Section: General Procedures For the Preparation Of The Diphosphanes 6a-cmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Inclusion of Copper(I) into a Novel Bipyridine-Containing Tetraphosphadiplatinacyclophane

Lindner

Veigel

Ortner

et al. 2000

Eur. J. Inorg. Chem.

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“…atoms are located in the center of the aliphatic bridges. [5] Some of these palladium-containing "nanometer-scale mo-Since the first typical metallaphanes appeared in the literalecular container compounds" are also capable of encapsuture in 1994, [6] investigations have been mainly focused on lating guest molecules. [10,11] two-dimensional systems.…”

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Cage-Structured Triplatinacyclophanes

Lindner¹,

Hermann

Baum

et al. 1999

Eur. J. Inorg. Chem.

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The synthesis of the tris(triflate) 4 (Scheme 1) has been achieved by means of a straightforward three‐step reaction sequence. After initial lithiation of mesitylene, treatment of the obtained trilithium compound C6H3(CH2Li)3 (2) with oxirane results in the formation of 1,3,5‐tris(3‐hydroxypropyl)benzene (3), which is then transformed to 4 by reaction with (CF3SO2)2O in the presence of pyridine. Whereas 4 reacts with Na2[Os(CO)4] in a somewhat complicated manner, similar reactions with Na[Re(CO)5] and LiPPh2 give the hydrocarbon‐bridged tris(rhenium) complex C6H3[(CH2)3Re(CO)5]3 (5) and the tris(phosphane) C6H3[(CH2)3PPh2]3 (6), respectively. Employing the high‐dilution method, from 6 and Cl2Pt(NCPh)2 the nanoscaled tri‐ and hexaplatinacyclophanes 7 and 9 are available. Owing to the optimal geometry and flexibility of the cage in 7, 1,2‐dichloroethane can be reversibly encapsulated. The molecular structure of 7 · 7 1,2‐Cl2C2H4 was determined by an X‐ray structure analysis. The utility of the reactive metal centers in 7 has been demonstrated by replacing the chloro ligands by acetonitrile to give the cationic platinacyclophane 8, in which, according to NMR studies, the cage‐like structure is preserved.

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Planar‐Chiral [7]Orthocyclophanes

et al. 2012

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Medium-sized bridged cyclophanes have attracted considerable interest because of their unusual conformational, chemical, and spectroscopic properties caused by deformation and strain in the aromatic ring and in the bridging ansa chain. [1] Among cyclophanes, meta-or paracyclophanes having dynamic planar chirality have generated much theoretical and synthetic interest as unique chiral molecules. In contrast, their regioisomer, that is, orthocyclophane (A) does not attract much attention owing to its less interesting topology and lack of planar chirality. [2] However, the introduction of a properly designed ansa chain, which can be on the outside of the plane of the benzene ring and decrease the flexibility of the molecule, may create stable planar chirality, even in simple orthocyclophanes. Herein we report the design and synthesis of the planar-chiral [7]orthocyclophanes 1 having an E alkene in the ansa chain, as well as a detailed stereochemical analysis and a demonstration of their utility in synthesis.Recently, we discovered a novel class of planar-chiral heterocycles (2) which consist of a bis(allylic) skeleton and the heteroatom X (X = O, NTs, SO n ; Ts= 4-toluenesulfonyl). [3] The chirality of these compounds originates from the presence of suitably located E and Z alkenes in the ninemembered ring. [4] On the basis of this stereochemical phenomenon, we anticipated that the orthocyclophane 1, in which the Z alkene of 2 is replaced by a benzene ring, may display planar chirality. It is also expected that 1 can achieve thermal stability, which 2 does not exhibit (see below). The details of the study are provided below.At the outset, we examined the synthesis of the nitrogencontaining orthocyclophane 1 aa (X = NTs, R = H) from the known diol 3 (Scheme 1). The Mitsunobu reaction of 3 and TsNHCO 2 Me proceeded with high group selectivity and provided the amide alcohol 4 as the only product in 78 % yield. [5] The Dess-Martin oxidation of the alcohol moiety of 4 followed by the Horner-Wadsworth-Emmons reaction and treatment with DIBAL provided the key intermediate (E)-5 in 71 % yield (three steps). The intramolecular Mitsunobu reaction of (E)-5 under a high dilution conditions (ca. 0.01m) provided the desired cyclic amide 1 aa in excellent yield (90 %). It should be noted that only a negligible amount of dimerized product (< 1 %) was formed in this reaction. The orthocyclophane 1 aa afforded a crystal suitable for X-ray analysis. The analysis reveals that the ansa chain is located on the outside of the plane of the benzene ring and both the benzene ring and alkene moieties of the ansa chain form chiral planes in the solid state (Scheme 1). [6] The existence of isolable enantiomers of 1 aa in solution was revealed by HPLC analysis using a chiral stationary column equipped with a CD spectropolarimeter. As shown in Figure 1, both enantiomers of 1 aa were successfully separated on an analytical as well as a semi-preparative scale. [7] The Scheme 1. Synthesis and X-ray analysis of 1 aa: a) TsNHCO 2 Me, PPh 3 , DEAD, TH...

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18‐, 20‐ und 22 gliedrige Dimetallaortho‐, ‐meta‐und ‐para[7.7]cyclophane ‐ die ersten typischen Metallaphane

Cited by 9 publications

References 16 publications

Inclusion of Copper(I) into a Novel Bipyridine-Containing Tetraphosphadiplatinacyclophane

Inclusion of Copper(I) into a Novel Bipyridine-Containing Tetraphosphadiplatinacyclophane

Cage-Structured Triplatinacyclophanes

Planar‐Chiral [7]Orthocyclophanes

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