It is possible to control the geometry and composition of metallasupramolecular assemblies via aspect ratio their ligands. This point demonstrated for a series iron- palladium-based coordination cages. Functionalized clathrochelate complexes with variable ratios were used as rod-like metalloligands. A cubic Fe(II)8L12 cage was obtained from metalloligand an intermediate ratio. By increasing length or by decreasing width ligand, self-assembly process resulted in clean formation tetrahedral...

Ditopic N-donor ligands with terminal 4-pyridyl groups are omnipresent in coordination-based self-assembly. The utilization of 3-pyridyl donor is significantly less common, because the intrinsic conformational flexibility these tends to favor formation small aggregates. Here, we show that large Pd6L1212+ cages can be obtained by reaction Pd(ii) salts metallo-ligands L bearing groups. easy-to-access contain an Fe(ii) clathrochelate core. These sterically demanding complexes prevent smaller...

We rationalize the behaviour of protonated merocyanines in water through cross-validation ¹H NMR, UV-Vis and pH measurements, show their capability to act as reversible photoacids along light/dark cycles can be described by a four-state model.

Four-electron reduction of dinitrogen has been achieved in the reaction N2 with [{p-But-calix[4]-(O)4}2Nb2(μ-M)2] (M = Li, 3; M Na, 4; K, 5), which contain a very reactive NbNb unit [NbNb 2.659(1) Å; 4], THF. The leads to dinuclear complexes [{p-But-calix[4]-(O)4}2(Nb⋮N−N⋮Nb)]2- M+2 6; 7; 8) [Nb⋮N 1.747(12) Å, N−N 1.390(17) 7], containing hydrazido [N2]4- anion. Two-electron tetraanion 7 using sodium metal nitrido species 11, [{p-But-calix[4]-(O)4}2Nb2(μ-N)2(μ-Na)2Na2], solution is...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMagnetic Properties Diagnostic for the Existence of Iron(II)-Iron(II) Bonds in Dinuclear Complexes Which Derive from Stepwise Insertion Reactions on Unsupported Iron-Aryl BondsAlain Klose, Euro Solari, Carlo Floriani, Angiola Chiesi-Villa, Corrado Rizzoli, and Nazzareno ReCite this: J. Am. Chem. Soc. 1994, 116, 20, 9123–9135Publication Date (Print):October 1, 1994Publication History Published online1 May 2002Published inissue 1 October...

N-Heterocyclic carbenes (NHCs) react at ambient conditions with nitrous oxide to give covalent adducts. In the crystal, all compounds show a bent N2O group connected via N-atom former carbene carbon atom. Most adducts are stable room temperature, but heating induces decomposition into corresponding ureas. Kinetic experiments that thermal stability of NHC-N2O depends on steric as well electronic effects. The coordination NHCs weakens N-N bond substantially, and facile rupture was observed in...

Ein guter Fang: N-heterocyclische Carbene (NHCs) bilden unter milden Reaktionsbedingungen stabile Addukte mit Distickstoffoxid (N2O). Die zeigen eine ungewöhnliche Reaktivität, wie am Beispiel einer Alkylierungsreaktion Spaltung der N-N-Bindung zu sehen ist. Detailed facts of importance to specialist readers are published as ”Supporting Information”. Such documents peer-reviewed, but not copy-edited or typeset. They made available submitted by the authors. Please note: The publisher is...

Multicomponent reactions between 1,4-benzenediboronic acid, catechol, and different pyridyl ligands are reported. The condensation of acid with catechol gives 1,4-bis(benzodioxaborole)benzene. Upon crystallization, the ester aggregates N-donor through dative B-N bonds. Depending on nature ligand, molecularly defined macrocycles or polymeric structures obtained. 1D polymers formed 4,4-bipyridine 1,2-di(4-pyridyl)ethylene, whereas a 2D network is obtained tetradentate ligand...

The reaction of cis-blocked, square-planar MII complexes with tetratopic N-donor ligands is known to give metallasupramolecular assemblies the formula M2nLn. These typically adopt barrel-like structures, paneling sides barrels. However, alternative structures are possible, as demonstrated by recent discovery a Pt8L4 cage unusual gyrobifastigium-like geometry. To date, factors that govern assembly MII2nLn not well understood. Herein, we provide geometric analysis M2nLn complexes, and discuss...

Cobalt(ii) complexes featuring hexadentate amino-pyridyl ligands have been recently discovered as highly active catalysts for the Hydrogen Evolution Reaction (HER), whose high performance arises from possibility of assisting proton transfer processes

ADVERTISEMENT RETURN TO ISSUEPREVCommunicationNEXTStepwise Reduction of Dinitrogen to Nitride Assisted by Niobium Bonded Oxygen Donor Atoms: The Potential Reduced Forms Calix[4]areneAntonio Zanotti-Gerosa, Euro Solari, Luca Giannini, Carlo Floriani, Angiola Chiesi-Villa, and Corrado RizzoliView Author Information Institut de Chimie Minérale et Analytique, BCH Université Lausanne CH-1015 Lausanne, Switzerland Dipartimento di Chimica, Università Parma I-43100 Parma, Italy Cite this: J. Am....

Photoinduced cleavage of the residual N-N bond in dimetallahydrazone 1 (Mes=2,4,6-Me3 C6 H2 ) led to a transient monomeric nitrido complex, which reacts further with form 2. Compound was synthesized by reductive arylation MoCl4 ⋅DME MesMgBr under an N2 atmosphere.

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTHydrazone Derivatives, an Efficient Class of Crystalline Materials for Nonlinear OpticsChristophe Serbutoviez, Christian Bosshard, Georg Knoepfle, Peter Wyss, Philippe Pretre, Guenter, Kurt Schenk, Euro Solari, and Gervais ChapuisCite this: Chem. Mater. 1995, 7, 6, 1198–1206Publication Date (Print):June 1, 1995Publication History Published online1 May 2002Published inissue 1 June...

The synthesis and characterization of a new class neutral aminyl radicals is reported. Monoradicals were obtained by reduction azoimidazolium dyes with potassium. Structural, spectroscopic, computational data suggest that the spin density centered on one nitrogen atoms former azo group. dimeric dye an octamethylbiphenylene bridge between groups resulted in formation biradical largely independent unpaired electrons. Both monoradicals found to display high stability solution as well solid state.

Crystalline networks based on dative boron–nitrogen bonds were obtained by combining polytopic N-donor ligands with polyboronic esters. The utilization of a tetrahedral boronate ester gave rise to sheet structure, whereas either linear polymer or diamond-like network was observed for ligand. intrinsic flexibility B←N linkages favors tight intermolecular packing and interpenetration in the crystalline state. Amorphous networks, other hand, found possess porosity BET surface areas up ∼300 m2...

2-Pyridylselenyl halides undergo facile coupling with a triple CN bond of unactivated nitriles.

Photoinduced cleavage of the residual N-N bond in dimetallahydrazone 1 (Mes=2,4,6-Me3 C6 H2 ) led to a transient monomeric nitrido complex, which reacts further with form 2. Compound was synthesized by reductive arylation MoCl4 ⋅DME MesMgBr under an N2 atmosphere.

The meso-octaethylporphyrinogen–sodium–lanthanide complexes, [{(η5 : η1 η5 η1-Et8N4)M}Na(thf)2], in the presence of Na metal and under a nitrogen atmosphere, fix reduce dinitrogen to [N2]2– anion, as shown by isolation dinuclear complexes containing [M(µ-η2 η2-N2)M] moiety [M = Pr, Nd].

This report details an extensive investigation on vanadium−dinitrogen complexes containing the [V(μ-N2)V]n+ skeleton with a variable oxidation state of metal and reduction degree dinitrogen, n varying from 6 → 5 4. can be associated to alkali cations in ion-separated or ion-pair tight forms. The reaction [(Mes)3V(thf)], 1 [Mes = 2,4,6-Me3C6H2], Lewis acids [AlPh3, B(C6F5)3] removed THF molecule leading under nitrogen formation diamagnetic complex [(Mes)3V(μ-N2)V(Mes)3], N2 also occurs...

ADVERTISEMENT RETURN TO ISSUEPREVArticleNEXTMigratory Aptitude of the Zr-C Functionalities Bonded to a Macrocyclic Structure: Thermally- and Solvent-Assisted Intra- Intermolecular Migrations in Dialkyl(dibenzotetramethyltetraazaannulene)zirconium(IV)Luca Giannini, Euro Solari, Stefania De Angelis, Thomas R. Ward, Carlo Floriani, Angiola Chiesi-Villa, Corrado RizzoliCite this: J. Am. Chem. Soc. 1995, 117, 21, 5801–5811Publication Date (Print):May 1, 1995Publication History Published online1...

Simply mixing the complex [{RuCl2(1,3,5-C6H3iPr3)}2] (1) with PCy3 is sufficient to generate a catalyst suitable for highly efficient atom-transfer radical addition and polymerization reactions at exceptionally low temperatures (see scheme). The steric congestion metal caused by bulky ligands thought be essential reactivity of catalyst. Supporting information this article available on WWW under http://www.wiley-vch.de/contents/jc_2002/2005/z462037_s.pdf or from author. Please note: publisher...

A bimetallic complex, in which a RuCl2(η2-C2H4)(PCy3) fragment is connected via three chloro bridges to (η6-p-cymene)RuCl2 fragment, has been synthesized and characterized by single-crystal X-ray crystallography. This complex was used catalyze the atom transfer radical addition of CCl4 CHCl3 olefins at temperatures between 0 40 °C. Turnover frequencies up 1550 h-1 were observed, making new one most active catalysts for this type reaction described so far.

A library of emission spectra 90 bis-cyclometallated iridium complexes has been obtained using a simple combinatorial approach performed at room temperature. Trends in maxima are rationalized Hammett parameters and invoking inter ligand energy transfer (ILET) processes. The screening allowed us to observe trends the broadness opening way for rational engineering colour purity molecular level. Finally limitations strategy discussed case study that involves two different monodentate ligands.

Abstract A new method for the synthesis of industrially important azoimidazolium dyes is presented. The procedure based on a reagent which rarely used in context synthetic organic chemistry: nitrous oxide (“laughing gas”). N 2 O first coupled to N‐heterocyclic carbenes. Subsequent reaction with aromatic compounds through an AlCl 3 ‐induced CH activation process provides good yields.

Polycarboxylate ligands are among the most important building blocks for synthesis of metal–organic frameworks (MOFs). The ability to access these in an efficient way is key importance future applications MOFs. Here, we demonstrate that mono- and dinuclear clathrochelate complexes versatile scaffolds preparation polytopic carboxylate ligands. largely inert have a trigonal-bipyramidal shape. functionalized clathrochelates with two, three, four, or five carboxylic acid groups ligand periphery...