Intramolecular diamination reactions are described which yield cyclic ureas as direct products of an oxidative alkene transformation in the presence palladium acetate and iodosobenzene diacetate terminal oxidant. The reaction is truly catalytic metal catalyst represents proof principle for this elusive type oxidation.

The first ansa-aminoborane N-TMPN-CH2C6H4B(C6F5)2 (where TMPNH is 2,2,6,6-tetramethylpiperidinyl) which able to reversibly activate H2 through an intramolecular mechanism synthesized. This new substance makes use of the concept molecular tweezers where active N and B centers are located close each other so that one molecule can fit in this void be activated. Because fixed geometry ansa-ammonium-borate it forms a short N−H···H−B dihydrogen bond 1.78 Å as determined by X-ray analysis....

Divide and conquer: Metal-free systems consisting of amines B(C6F5)3 cleave H2 heterolytically at ambient pressure often room temperature. The efficient reduction benzaldehyde by the product shown in scheme highlights potential such for application hydrogenation reactions.

A series of highly luminescent dinuclear copper(I) complexes has been synthesized in good yields using a modular ligand system easily accessible diphenylphosphinopyridine-type P^N ligands. Characterization these via X-ray crystallographic studies and elemental analysis revealed complex structure with butterfly-shaped metal-halide core. The feature emission covering the visible spectrum from blue to red together high quantum up 96%. Density functional theory calculations show that HOMO...

Abstract Easy come, easy go: the great structural diversity of Cu I complexes is an ambivalent trait. Apart from well‐known catalytic properties , a number potent luminescent have been found in last ten years featuring plethora motifs. The downside this variety undesired formation other species upon processing. In here, strategies to avoid behavior are presented: Only one favorable unit often exists for multinuclear with bridging ligands. addition, these exhibit photophysical due cooperative...

A series of highly luminescent, heteroleptic copper(I) complexes has been synthesized using a modular approach based on easily accessible P^N ligands, triphenylphosphine, and halides, allowing for an independent tuning the emission wavelength with low synthetic efforts. The molecular structure investigated via X-ray analysis, confirming dinuclear complex consisting butterfly shaped metal-halide cluster two different sets ligands. bidentate ligand bridges metal centers can be used to tune...

An open form of a 2,4-diphosphabicyclobutane is one way to describe the unprecedented structure P2C2 heterocycle 1 (Ar = 2,4,6-tBu3C6H2). Ab initio calculations on show that partially delocalized π system exists with considerable diradical contribution. Dark red accessible from ArP  CCl2 and nBuLi.

We report the synthesis of six new dendrimers built around a [Ru(bpy)3]2+-type core (bpy = 2,2'-bipyridine) and bearing up to 24 4'-tert-butylphenyloxy or 48 benzyl units in periphery. The metallodendrimers were obtained by complexation ruthenium trichloride Ru(bpy)2Cl2 with bipyridine ligands carrying dendritic wedges 4,4'-positions. absorption spectra luminescence properties (spectra lifetimes at 77 298 K; quantum yields K) novel compounds are reported. All them show characteristic unit....

An efficient organometallic gelator can gel a variety of organic solvents even in concentrations as low 0.2 wt %. π Stacking the heteroarene moieties, van der Waals interactions between alkyl chains, and metal–metal may be responsible for aggregation. This palladium pincer bis(carbene) complex (see scheme) is first air-stable low-molecular-mass that reveals promising catalytic activity state. Supporting information this article available on WWW under...

Abstract New highly active ansa ‐ammonium borate catalysts for the direct metal‐free hydrogenation of imines were prepared by tuning basicity and steric bulkiness their amine moieties. The highest catalytic activity among previously reported organocatalytic systems was shown a wide range nitrogen‐containing substrates. first example asymmetric imine based on concept demonstrated. Furthermore, effective catalyst recovery extraction acidic solution with an organic solvent followed dehydration...

Strongly luminescent, neutral copper(I) complexes bearing 5-(2-pyridyl)tetrazolate and various phosphine ligands were synthesized. While the cationic precursors 1b-4b do not exceed photoluminescence quantum yields (PLQY) of 4-46%, 1a-4a show PLQYs up to 89%.

We report the synthesis and reactivity of a chiral aminoborane displaying both rapid reversible H2 activation. The catalyst shows exceptional in asymmetric hydrogenation enamines unhindered imines with stereoselectivities up to 99% ee. DFT analysis reaction mechanism pointed importance repulsive steric stabilizing intermolecular non-covalent forces stereodetermining hydride transfer step catalytic cycle.

Organic light-emitting diodes (OLEDs) are currently being commercialized for lighting and display applications, but more work has to be done. In addition the ongoing optimization of materials devices in terms efficiency lifetime, substitution processing steps involving vacuum deposition solution techniques is favorable. To reach this aim, good soluble required. A modular family highly emissive PyrPHOS-copper iodide complexes featuring various ancillary phosphine ligands been synthesized....

Abstract Novel copper(II) 2‐ N ‐arylpyrrolecarbaldimine‐based catalysts for the aerobic oxidation of benzylic alcohols mediated by 2,2,6,6‐tetramethylpiperidine‐1‐oxyl (TEMPO) radical are reported. The catalytic activity both synthesized and in situ made complexes alkaline water solutions was studied revealing high efficiency selectivity (according to GC always >99%) these systems. For example, quantitative conversion benzyl alcohol benzaldehyde can be achieved with prepared bis[2‐...

C-H borylation is a powerful and atom-efficient method for converting affordable abundant chemicals into versatile organic reagents used in the production of fine functional materials. Herein we report facile aromatic olefinic bonds with 2-aminophenylboranes. Computational experimental studies reveal that metal-free insertion proceeds via frustrated Lewis pair mechanism involving heterolytic splitting bond by cooperative action amine boryl groups. The adapted geometry reactive B N centers...

Two 2-[bis(pentafluorophenyl)boryl]-N,N-dialkylanilines reported here exemplify a new class of intramolecular frustrated B/N Lewis pairs. A structure closely related to this was synthesized in 2003 by Piers et al. but unable activate H2. The aminoboranes can hydrogen at near ambient conditions; besides, one them hydrogenate imines and enamines catalytic fashion demonstrating the validity original Piers' approach activation with ansa-aminoboranes.

Elevated by the support: 2-Alkynyl aniline cycloisomerization to indole is catalyzed cationic Au NPs on a carbon support. Electroneutral and rich 2-aryl indoles are further converted into 3,3′-biindoles oxidative homocoupling that readily carbon, exclusively but also somewhat sluggishly As service our authors readers, this journal provides supporting information supplied authors. Such materials peer reviewed may be re-organized for online delivery, not copy-edited or typeset. Technical...

Bridging P(^)N ligands bearing five-membered heterocyclic moieties such as tetrazoles, 1,2,4-triazoles, oxadiazoles, thiadiazoles, and oxazoles have been investigated regarding their complexation behavior with copper(I) iodide metal salts. Different complex structures were found, depending either on the ligand itself or ligand-to-metal ratios used in reaction. Two different kinds of luminescent dinuclear a kind tetranuclear structure revealed by X-ray single-crystal analyses further for...

To explore their suitability for applications in molecular optoelectronics and as sensory materials, novel dithieno[3,2-b:2',3'-d]phospholes have been synthesized reactivity properties investigated. An efficient two-step synthesis allowed a modular assembly of differently functionalized compounds. The dithieno[3,2-b:2',3'-d]phosphole system exhibits extraordinary optoelectronic with respect to wavelength, intensity, tunability. Owing the nucleophilic nature central phosphorus atom, its...

A 20% yield (!) of new knot-shaped molecules with amide structure is surprisingly obtained from simple building blocks in a one-step synthesis. The molecular confirmed by X-ray analysis. centrosymmetric unit cell and attempts at chromatographic enantiomeric separation on chiral column material reveals that the trefoil knot (see picture) is, as expected, topologically chiral, although it does not contain any common elements such stereocenters.

A variety of differently substituted 1,3,2-diazaphospholenium salts and P-halogeno-1,3,2-diazaphospholenes (X = F, Cl, Br) were synthesized, their molecular structures, bonding situation, Lewis acid properties characterized by experimental (single-crystal X-ray diffraction, NMR IR/Raman spectroscopy, MS, conductometry, titrations with bases) computational methods. Both investigations confirmed that the structure in diazaphospholenium cations OTf BF4 resembles neutral Arduengo carbenes should...

Ungleiche Teilung: Metallfreie Systeme aus Aminen und B(C6F5)3 bewirken bei moderatem Druck teilweise schon Raumtemperatur die einfache heterolytische Spaltung von H2. Die effiziente Reduktion Benzaldehyd durch das Produkt dieser Reaktion (siehe Schema) weist auf Potenzial solcher für Anwendung in Hydrierungen hin. Supporting information for this article is available on the WWW under http://www.wiley-vch.de/contents/jc_2001/2008/z800935_s.pdf or from author. Please note: The publisher not...

The cation 4 can be obtained in an amazingly simple raction sequence from phosphorus trichloride 1 and the arylamine 2 via iminophosphane 3. Spectroscopic findings—δ(31P) = 79.3—and structural data—PNC angle 177°, PN distance 147.5 pm—suggest presence of a triple bond, whereby is isoelectronic with :SiN–aryl.

Enlarged scope by fluorinated mediators: Oxyl radicals are easily formed on boron-doped diamond (BDD) electrodes and can be exploited for the ortho-selective coupling to corresponding biphenols (see scheme). At partial conversion, a clean transformation is achieved that applied electron-rich as well phenols.