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

Adams, Florian; Gompper, Rudolf

doi:10.1002/ange.19891010814

Cited by 10 publications

References 28 publications

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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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Template synthesis of polyazamacrocyclic compounds

Gérbéléu

Arion

Burgess

1999

Template Synthesis of Macrocyclic Compounds

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Metallkomplexe unsymmetrisch überbrückter [N₄]‐Makrocyclen: Synthese, Struktur und Redoxverhalten

et al. 1995

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Metal Complexes of Unsymmetrically Bridged IN4] Macrocycles: Synthesis, Structure and Redox BehaviourMetal complexes M-5a (M = Cu, Ni, CO, Fe, and I-Fe") of 6,13-Di(ethoxycarbonyl)-7,12-dimethyl-benzo[ b]-l,4,8,11tetraaza-cyclotetradeca-2,5,7,11,13-pentaene and the free ligand H2-5a have been synthesized. The crystals of Cu-5a . H20 and Ni-5a . H 2 0 consist of planar complex molecules which are linked by H bridges between the water molecules and the peripheric ester groups to give 1D chains. The average M-N-distances are equal for both complexes (Cu 1.928, Ni 1.924 A), being unexpectedly large for the nickel complex. 'The redox properties of all the new compounds as well as some acetyl derivatives M-5b have been examined by cyclic voltammetry and compared with those of the previously re-ported symmetrically phenylene (M-4) and ethylene (M-6) bridged derivatives. All complexes give a reversible single electron reduction which clearly shows the increasing electron density around the central atom in the order M-4 < M-5 < M-6. Like the carbonyl substituted tetraazaannulenes M-4 the copper complexes Cu-5 give two, the cobalt complexes CO-5 three, and the iron complex Fe-5a probably four reversible single electron oxidations. They can be attributed to the species [M"'L-I']+, (M"L0J2+, [M"1Lo]3f, and [Fe1VLo]4+ with Lo being a "non innocent" neutral 1,2-quinodiimine ligand. Very surprisingly, since in contrast to Ni-4 and Ni-6, the nickel complexes Ni-5 gave no reversible oxidation. Makrocyclisch [Ni-1-koordinierte Chelatkomplexe der 3d-Elemente wirken als Aktivzentren vieler Biokatalysatoren. Beispiele sind das allen Hamenzymen zugrunde liegende Eisenporphyrin 1, das Corrin 2 der B12-Enzyme und das Dihydrocorphingeriist 3 des Cofaktors F 430[']. Obwohl sie fur unterschiedlichste Prozesse der biologischen Stoff-und Energiewandlung funktionsoptimiert sind, zeigen sie eine Reihe ubereinstimmender Strukturmotive, die offenbar gunstige Voraussetzungen fur eine Steuerung der katalytischen Eigenschaften biecen: Das Zentraiion bildet mit dem Bquatorial koordinierten, anionischen [N4]-Liganden mindestens zwei konjugiert-ungesattigte Chelatsechsringe aus. Hinsichtlich des x-Elektronensystems und der Ringgliederzahl m des inneren Makrocyclus sowie der Ladung z des Ligandanions bestehen charakteristische Unterschiede (1: 18 n; m = 16, z = -2; 2: 14 x; m = 15, z = -1; 3: 12 x; m = 16, z = -1). Die fur das Design biomimetischer Katalysatoren wichtige Frage, wie derartige Strukturmerkmale das katalytische Leistungsvermogen und die dafur entscheidenden Eigenschaften solcher Komplexe beeinflussen, 1al3t sich bisher kaum beantworten. Vor 30 Jahren erhielten wir uber eine Templatsynthese erstmals Komplexe des ,,Tetraaza[14]annulen6'-Typs 4, die sich von cyclischen 2:2-Kondensationsprodukten aus p-Dicarbonylverbindungen und 1,2-Phenylendiamin ableitenL'1. Sie unterscheiden sich vom inneren Makrocyclus des Por-1 4 4-8 I R' R2 R3 2 R2 5 X=C2H, p 3 R3&R1 / N \ A X M X ' 6 phyrinsystems nur durch das Fehlen zweier Methingruppen (16 n; m = 14...

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ChemInform Abstract: Di(4‐pyridinio)‐, Di(2‐benzothiazolio)‐, Di(2‐(1,3‐dithiolylio))‐, and Diformyltetraaza(14)annulenes and Tetraaza(14)annulenylene‐Homologous Tetrathiafulvalenes.

Adams¹,

Gompper²

1989

ChemInform

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ChemInform Abstract Following investigations on derivatives with N-linked substituents (cf. the preceding abstract), tetraazaannulenes linked to a C atom of the substituent are prepared; they represent potential new donors for the preparation of organic superconductors. The initial products of type (III) can be deprotonated to yield 7,16-bismethylene derivatives such as (IV) and (VI), compound (VIb) being the homologue of tetrathiafulvalene. Further derivatives (VIIIb)-(VIIId) are accessible via (VIIIa) (metal complexes of (III) and (VIII) are prepared as well), but an attempted synthesis of analogues of (VI) possessing cyanide functions instead of the benzo annulation rather leads to open-chain products. While (VIb) fails to react with p-tetracyanoquinodimethane, all compounds (VI) yield black complexes of the composition (VI)•(I3)1.7 on treatment with iodine; the conductivity of these complexes is insignificant ranging from 1.7•10-10 to 1.3•10-9 S cm-1.

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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

Cited by 10 publications

References 28 publications

Template synthesis of polyazamacrocyclic compounds

Template synthesis of polyazamacrocyclic compounds

Metallkomplexe unsymmetrisch überbrückter [N₄]‐Makrocyclen: Synthese, Struktur und Redoxverhalten

ChemInform Abstract: Di(4‐pyridinio)‐, Di(2‐benzothiazolio)‐, Di(2‐(1,3‐dithiolylio))‐, and Diformyltetraaza(14)annulenes and Tetraaza(14)annulenylene‐Homologous Tetrathiafulvalenes.

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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

Cited by 10 publications

References 28 publications

Template synthesis of polyazamacrocyclic compounds

Template synthesis of polyazamacrocyclic compounds

Metallkomplexe unsymmetrisch überbrückter [N4]‐Makrocyclen: Synthese, Struktur und Redoxverhalten

ChemInform Abstract: Di(4‐pyridinio)‐, Di(2‐benzothiazolio)‐, Di(2‐(1,3‐dithiolylio))‐, and Diformyltetraaza(14)annulenes and Tetraaza(14)annulenylene‐Homologous Tetrathiafulvalenes.

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Metallkomplexe unsymmetrisch überbrückter [N₄]‐Makrocyclen: Synthese, Struktur und Redoxverhalten