Synthesis of superstructure ligands using a novel methyl vinyl ether functional group

Schammel, Wayne P.; Zimmer, L. Lawrence; Busch, Daryle H.

doi:10.1021/ic50212a066

Cited by 21 publications

(12 citation statements)

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“…The reagent (7,8) is the novel methoxyethylidene-substituted macrocycle (structure 6) first reported from these laboratories several years ago. It is formed by the reaction of the well-known Jger complex (structure 5) with a strong methylating agent, equation 1.…”

Section: General Synthetic Procedures For the Dry Cave Ligandsmentioning

confidence: 99%

“…This reaction closely parallels amide formation by carboxylate esters and may be rationalized on the basis of the electron withdrawing effect of the metal ion on the vinyl group. The ring closure reactions are naturally efficient because of the conformation of the methoxyethylidene reagent (8,9). Looking to structure 6, the unsaturated chelate rings rise up on the same side of the NiN4 plane (x-ray structure, ref.…”

Section: General Synthetic Procedures For the Dry Cave Ligandsmentioning

confidence: 99%

“…This is implied in structure 3 and is generally expected on the simplest of steric grounds. The formation of the dimer brings very bulky groups into juxtaposition and it has been shown that bulky groups favor the lid-on position (8). This has been combined with a specific feature of the '3C nmr spectra to provide a very convenient preliminary identification technique for the isomers in cases where R2 and R3 are both CH3.…”

Section: The Dimeric Bimetallic Complexesmentioning

confidence: 99%

“…For the lid-on dimers, the resonances for these two carbon atoms are separated by about 5-6 ppm and occur near 15-16 and 20-21 ppm from TMS. In the site of deprotonation was demonstrated using derivatives of nonbridging amines (8). The bridged complexes for which R1 = (CH2)4 and m-xylyl serve to illustrate the behavior of these species.…”

Section: The Dimeric Bimetallic Complexesmentioning

confidence: 99%

“…The unbridged complex (CH3,H,(CH3)2) can be caused to undergo partial rearrangement of the corresponding pentadentate ligand by subjecting its CO derivative to rearrangement conditions (equation 8) the CO stretching frequency occurs at 1989 cm '. (8) cI The Fe2+/Fe3+ couple for the partially rearranged m-xylene derivative occurs at -O.25V causing it and its homologs to be slightly less sensitive to oxygen than their cave counterparts.…”

Section: Products Of Partial Rearrangementmentioning

confidence: 99%

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Multiple structures from a macro bicyclization reaction - the rich chemistry of the Jager macrocycles

Busch¹

1980

Pure and Applied Chemistry

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-The well developed synthetic system for preparation of a highly versatile family of 4ycave ligands has yielded two other very different families of equally interesting ligands.The 4ycave ligands are designed to provide a protected coordination site for such small molecules as CO and 02. The second family of ligands is related to the first by dimerization and the resulting complexes contain two identical metal ions separated by an intramolecular void. An intramolecular tautomerization reaction of the coordinated 4y cave ligand produces a unique family of clathro-chelate structures in which the metal ion is totally encapsulated by a hexadentate ligand, containing azomethine donor groups.The development of the chemistry of complexes with macrocyclic ligands has received continuing impetus from the biochemistry of such macrocycle-containing systems as heme proteins, vitamin B12 and siderophores and ionophores. Our interest in mimicking the various functions of the heme proteins has been further stimulated by the compelling potential applications of controlled oxidation reactions of organic molecules. Studies in a number of laboratories on substituted porphyrins have clearly shown that appended structural components (superstructure) can serve, in place of the protein, to control the chemistry at the active site in the heme protein. We have recently reported (1) a very promising new series of bicyclic 4y cave ligands (structure 1) that has been designed to provide a protected cavity for the binding of such small molecules as 02 and CO. The ligands resemble porphrins only in that they contain four nitrogen donors NR2 = (CH2)n, n = 4-8, m-, p-xylyl, etc.

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Section: General Synthetic Procedures For the Dry Cave Ligandsmentioning

confidence: 99%

Section: General Synthetic Procedures For the Dry Cave Ligandsmentioning

confidence: 99%

Section: The Dimeric Bimetallic Complexesmentioning

confidence: 99%

Section: The Dimeric Bimetallic Complexesmentioning

confidence: 99%

Section: Products Of Partial Rearrangementmentioning

confidence: 99%

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Multiple structures from a macro bicyclization reaction - the rich chemistry of the Jager macrocycles

Busch¹

1980

Pure and Applied Chemistry

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Template synthesis of polyazamacrocyclic compounds

Gérbéléu

Arion

Burgess

1999

Template Synthesis of Macrocyclic Compounds

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Compounds containing nitrogen in their cyclic backbone are one of the most representative groups of macrocyclic systems, and are very often synthesised by template reactions. The ligsons participating in the construction of ligand products must have certain groups or positions in moleculeswhich are sometimes concealed, revealing themselves when coordinated and activated by the template.Building up polyazamacrocyclic systems on the appropriate matrices is carried out by the interaction of compounds containing amine or imine groups with aldehydes, ketones, organic halogen derivatives, substituted malonic esters and ligsons containing unsaturated C-C bonds. The process may also be performed by interaction of the appropriate blocks, containing both functional groups necessary for obtaining the final product. Among such template reactions the most frequent is the formation of azomethine construction bonds, then C-N and C-C and in some cases, N=N chelatogene bonds.

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Di(4‐pyridinio)‐, Di(2‐benzothiazolio)‐, Di(2‐[1,3‐dithiolylio])‐ und Diformyl‐tetraaza[14]annulene sowie Tetraaza[14]annulenylen‐homologe Tetrathiafulvalene

Adams¹,

Gompper²

1989

Angewandte Chemie

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Ein Weg zu neuen Donoren für die Gewinnung organischer Metalle und Supraleiter könnte über die Titelverbindungen führen. Anders als beim vorstehenden Beitrag sind die kationischen Substituenten in 1 (siehe oben) über ein C‐Atom mit dem Ring verknüpft. Beim nebenstehenden Deprotonierungsprodukt mit X   S  CH  CH  S  handelt es sich um ein Homologes des „Parade‐Donors”︁ Tetrathiafulvalen.

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Synthesis of superstructure ligands using a novel methyl vinyl ether functional group

Cited by 21 publications

References 0 publications

Multiple structures from a macro bicyclization reaction - the rich chemistry of the Jager macrocycles

Multiple structures from a macro bicyclization reaction - the rich chemistry of the Jager macrocycles

Template synthesis of polyazamacrocyclic compounds

Di(4‐pyridinio)‐, Di(2‐benzothiazolio)‐, Di(2‐[1,3‐dithiolylio])‐ und Diformyl‐tetraaza[14]annulene sowie Tetraaza[14]annulenylen‐homologe Tetrathiafulvalene

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