A Facile Route to Aryl Boronates: Room‐Temperature,Copper‐Catalyzed Borylation of Aryl Halides with Alkoxy Diboron Reagents

A simple but effective copper‐catalyzed borylation of aryl halides, including electron‐rich and sterically hindered aryl bromides, with alkoxy diboron reagents occurs under mild conditions (see scheme). Preliminary DFT studies of the mechanism suggest that σ‐bond metathesis between a copper–boryl intermediate and the aryl halide generates the aryl boronate product.

     

Efficient photoacids based upon triarylamine dialkylsulfonium salts

New triarylamine dialkylsulfonium salts that are photosensitive in the near-ultraviolet have been prepared. The quantum yields of photoacid generation were found to be approximately 0.5 and are independent of the counterion. On the other hand, the efficiencies of the sulfonium salts toward the photopolymerization of cyclohexene oxide depend on the counterion and the sulfonium substituents. Photopolymerization kinetic studies demonstrate that these triphenylamine sulfonium salts are highly efficient cationic photoinitiators.     

Synthesis, characterisation and molecular structure of [Rh(COE)2(acac)] (COE=cyclooctene, η-C8H14), an important starting material for the preparation of rhodium catalyst precursors

The compound [Rh(COE)₂(acac)] (1) is a catalyst precursor in its own right, and a starting material for the preparation of other catalyst precursors for use in a variety of reactions such as hydroboration, diboration and the addition of arylboronic acids to aldehydes. Although a preparation using Tl(acac) and [Rh(COE)₂(μ-Cl)]₂ is in the literature, it would appear that it is not widely known and we have received several requests for our synthetic protocol for 1, which does not use any thallium salts. We present herein a synthesis of 1 from [Rh(COE)₂(μ-Cl)]₂ and Na(acac), along with its full spectroscopic and structural characterisation. The single crystal X-ray structure of 1 indicates approximate square-planar geometry at Rh, with the two olefinic CC bonds lying perpendicular to the square plane.     

An anionic organic mixed-valence system with a remarkably well-resolved vibrational structure in its intervalence band

The reduction of a phenylene-bridged bis(dioxaborine) affords a strongly delocalised organic mixed-valence system; for the first time details of the vibrations coupled to the electron transfer have been extracted from the intervalence band.     

Platinum catalysed 3,4- and 1,4-diboration of alpha,beta-unsaturated carbonyl compounds using bis-pinacolatodiboron

Bis-pinacolatodiboron reacts with [small alpha],[small beta]-unsaturated carbonyl compounds to give 1,4- and unprecedented 3,4-additions in the presence of a second generation Pt(0) catalyst at ambient temperature.     

Aromatic amines: a comparison of electron-donor strengths

The electron-donor abilities of ten aminophenyl systems and an additional aminothienyl system are compared using density functional theory calculations. The systems studied here include those with amine nitrogen atoms bearing alkyl or aryl groups and those with amine nitrogen atoms as part of a heterocycle. Their abilities to act as donors in electron-transfer processes are assessed from calculated vertical ionization potentials for the aminobenzenes, which are in good agreement with available experimental data. Their abilities to act as intramolecular pi-electron donors in conjugated systems are inferred from the bond lengths and charge densities calculated for the corresponding 4-aminobenzaldehydes and 4-aminobenzonitriles. The computed (13)C NMR chemical shifts for the 4-aminobenzaldehydes and 4-aminobenzonitriles are in good agreement with published and new experimental data. The chemical shifts correlate well with the computed charge densities and can, to some extent, be used as an experimental probe of pi-donor strength. We find that the electron-transfer-donor strengths do not correlate well with pi-donor strengths: these differences can largely be attributed to steric effects.     

A fluorine-substituted hexakisdecyloxy- hexa-peri-hexabenzocoronene

[structure: see text] The first fluorine-substituted hexabenzocoronene has been synthesized and is much more readily reduced than its nonfluorinated analogues. Thin films of this material show columnar order at room temperature, and the charge-carrier mobility measured by the pulse-radiolysis time-resolved microwave conductivity technique is comparable to that of other hexabenzocoronene materials.     

Photorefractive polymers sensitized by two-photon absorption

We demonstrate the recording of holograms and their nondestructive readout in a photorefractive polymer, using two-photon absorption. Sensitivity is provided by the excitation of the electroactive chromophore with femtosecond pulses, followed by charge injection into the photoconducting poly(N -vinylcarbazole) matrix. The holograms can be fully erased with a pulsed laser source but are insensitive to cw laser beams with the same wavelength. Studies of the field and intensity dependence of the diffraction efficiency indicate that the holograms are formed through the photorefractive effect.     

Bromination Improves the Electron Mobility of Tetraazapentacene

A cyclocondensation of TIPS‐ethynyl‐substituted diaminoarenes with in situ obtained 4,5‐dibromocyclohexa‐3,5‐diene‐1,2‐dione has led to the synthesis of tetrabromotetraazapentacene (BrTAP). BrTAP is easily reduced to its air‐stable radical anion and electron mobilities >0.56 cm² V^?1 s^?1 can be achieved in thin‐film transistors.