Synthesis, Structure, and Properties of an Intramolecularly Coordinated Diindacycle:  9,10-Dihydro-9,10-bis[2,6-bis((dimethylamino)methyl)- phenyl]-9,10-diindaanthracene

Abstract

o-Phenylenemagnesium (1) was used to prepare the first structurally characterized intramolecularly coordinated diindacycle: 9,10-dihydro-9,10-bis[2,6-bis((dimethylamino)methyl)phenyl]-9,10-diindaanthracene (3).

Travelling the organometallic road: a Wittig student’s journey from lithium to magnesium and beyond

“…The crystal structure showed a slightly distorted tetrahedron of 4 magnesium atoms with each triangle of the tetrahedron capped by a phenylene unit in such a fashion that one carbon is s-bonded to one magnesium and the second carbon is m-bridging between two other magnesiums (Scheme 6; only one phenylene unit shown). Similar tetrameric structures were found for 1,2-diphenylvinylenemagnesium ( 18) and the 1,3-dimagnesium derivative 1,8-naphthalenediylmagnesium (19). These tetrameric structures are reminiscent of those of many organolithium compounds.…”

“…According to NMR spectroscopy in [D 8 ]THF, single species were obtained for R = Me or Et and mixtures of species for R = t-Bu, Ph and of organyl groups capable of intramolecular coordination (Scheme 8); though crystals formed, they easily crumbled so that X-ray structures could not be obtained. 18 Very probably, some of these species are of the dihydroanthracene type observed for 20b (vide supra) and for the heavier metals of Group 13 in the case of gallium (21) and indium (22); in the crystal, both 21 18 and 22 19 have an essentially planar central ring (Scheme 9).…”

Perfluorinated Diindacycles

“…By application of this latter concept, efficient mercury-based anion receptors with electron-withdrawing backbones have been discovered. ,, We have recently synthesized 9,10-dibromo-9,10-dihydro-9,10-diindaanthracene ( 1 ) . As a result of the unique spatial arrangement of the two indium centers, this diindacycle behaves as a versatile bifunctional Lewis acid, which can be used both as a Lewis acidic spacer and as a selective bidentate receptor for nucleophiles . With the prospect of increasing the Lewis acidity of the indium centers, we endeavored to prepare perfluorinated analogues of 1 .…”

Synthesis of a Diindacycle by Transmetalation of 1,8-Bis(trimethylstannyl)naphthalene with InCl3

“…Group 13 polyfunctional Lewis acids are becoming useful in the field of catalysis, − molecular recognition, − and material synthesis. , While a large amount of work has focused on the use of boron 1-4,8,11,12 ,,, and aluminum 5-7,10,13,17 ,,, at the active site of these derivatives, recent efforts have been concerned with the preparation of derivatives containing several indium centers. ,− Such compounds are useful derivatives that can serve as selective molecular hosts 14 and supramolecular building blocks . The discovery of high-yield syntheses leading to this class of compound has remained one of the main challenges.…”