Assembly of organosilver coordination frameworks with aromatic ligands bearing a terminal enediyne group
摘要:
In a series of five silver(I) complexes synthesized with (2-ethynylbut-1-en-3-yne-1,1-diyl)dibenzene (H(2)L1) and 9-(penta-1,4-diyn-3-ylidene)-9H-fluorene (H2L2), each resulting ethynide ligand is invariably inserted into a Ag-n (n = 3-4) basket, leading to the generation of coordination chains or multinuclear metallocycles, but the well shielded ethenyl group does not take part in silver-olefin binding. In (Ag(2)L1)center dot 9AgCF(3)CO(2)center dot 3H(2)O center dot 3CH(3)CN and (Ag(2)L1)(2)center dot 9AgCF(3)CO(2).11H(2)O, which can be crystallized in different polar protic solvent media, an infinite chain composed of metallocycles is favorably generated with the assistance of silver-aromatic interaction; such chains are further interconnected to form a two- or three-dimensional organosilver network. In (Ag2L2)center dot 5AgCF(3)CO(2)center dot 5DMSO, the fluorenyl group does not participate in silver-aromatic interaction; however, its planar skeleton directs the construction of a more closely packed metal-organic coordination chain. (C) 2013 Elsevier Ltd. All rights reserved.
Reductive Bergman-Type Cyclizations of Cross-Conjugated Enediynes to Fulvene and Fulvalene Anions: The Role of the Substituent
作者:Noach Treitel、Lior Eshdat、Tuvia Sheradsky、Patrick M. Donovan、Rik R. Tykwinski、Lawrence T. Scott、Henning Hopf、Mordecai Rabinovitz
DOI:10.1021/ja0566477
日期:2006.4.1
Various cross-conjugated enediynes undergo "Bergman-type" cycloaromatizations upon reduction with potassium metal, generating anions of fulvenes and fulvalene derivatives. This new anionic cyclization is considerably more facile than the classic Bergman cyclization with linear enediynes, creating highly reactive diradicals at -78 degrees C. Not all cross-conjugated enediynes yield cyclized dianions
Electrochromic Application of an Enediyne Scaffolding as a Redox-Active Chromophore− Synthesis and Redox Behavior of 9,10-Bis[3-(6-azulenyl)-1-(6-azulenylethynyl)-2-propynylidene]-9,10-dihydroanthracenes
A bis(enediyne) system utilizing anthraquinodimethane as a platform for a redox-active substructure that bears azulenes as π-electron-accepting groups at the periphery has been prepared by a simple one-pot reaction involving repeated Pd-catalyzed alkynylation of 6-bromoazulenes with the bis(enediyne). The novel bis(enediyne)s exhibited two, one-step two-electron redox properties under electrochemical