A mixed‐valence chloride‐bridged (pincer)IrIII–(diene)IrI complex

The title compound, [2,6‐bis(di‐tert‐butylphosphino)phenyl‐1κ³P,C¹,P′]di‐μ‐chlorido‐1:2κ⁴Cl:Cl‐(2η⁴‐cycloocta‐2,5‐diene)hydrido‐1κH‐diiridium(I,III) hexane hemisolvate, [Ir₂(C₈H₁₂)(C₂₄H₄₃P₂)Cl₂H]·0.5C₆H₁₄ or [(^tBuPCP)IrH(μ₂‐Cl)₂Ir(COD)][^tBuPCP is κ³‐2,6‐(^tBu₂PCH₂)₂C₆H₃ and COD is η⁴‐2,5‐cyclooctadiene], is an Ir^III/Ir^I dimer bridged by two chloride ions. The Ir₂Cl₂ framework is nearly planar, with a dihedral angle of 13.04 (4)° between the two Ir centers. The compound was isolated as a hexane hemisolvate. A list of distances found in Ir(PCP) compounds is given.     

Experimental and theoretical studies of charge transfer and deuterium ion transfer between D2O+ and C2H4

The charge transfer and deuterium ion transfer reactions between D(2)O(+) and C(2)H(4) have been studied using the crossed beam technique at relative collision energies below one electron volt and by density functional theory (DFT) calculations. Both direct and rearrangement charge transfer processes are observed, forming C(2)H(4) (+) and C(2)H(3)D(+), respectively. Independent of collision energy, deuterium ion transfer accounts for approximately 20% of the reactive collisions. Between 22 and 36 % of charge transfer collisions occur with rearrangement. In both charge transfer processes, comparison of the internal energy distributions of products with the photoelectron spectrum of C(2)H(4) shows that Franck-Condon factors determine energy disposal in these channels. DFT calculations provide evidence for transient intermediates that undergo H/D migration with rearrangement, but with minimal modification of the product energy distributions determined by long range electron transfer. The cross section for charge transfer with rearrangement is approximately 10(3) larger than predicted from the Rice-Ramsperger-Kassel-Marcus isomerization rate in transient complexes, suggesting a nonstatistical mechanism for H/D exchange. DFT calculations suggest that reactive trajectories for deuterium ion transfer follow a pathway in which a deuterium atom from D(2)O(+) approaches the pi-cloud of ethylene along the perpendicular bisector of the C-C bond. The product kinetic energy distributions exhibit structure consistent with vibrational motion of the D-atom in the bridged C(2)H(4)D(+) product perpendicular to the C-C bond. The reaction quantitatively transforms the reaction exothermicity into internal excitation of the products, consistent with mixed energy release in which the deuterium ion is transferred in a configuration in which both the breaking and the forming bonds are extended.     

Parallel separations of oligonucleotides with optically gated sample introduction on multichannel microchips

With the release of the human genome sequence, there has been increasing attention given to other genetic analyses, including the detection of genetic variations and fast sequencing of multiple samples for pharmacogenomics studies. Rapid injections of samples in multiplexed separation channels by optically gated sample introduction are shown here for DNA separation. Serial separations of four amino acids are shown in less than four seconds on a microchip with four multiplexed channels. Five short oligonucleotides have also been rapidly separated in 2% LPA with four channels using this technique. In addition, multiple unique samples have been simultaneously separated and five-base resolution has been demonstrated.     

A novel effective electrophile: β-trifluoroacetylketene diphenyldithioacetal S,S-tetroxide

A synthesis of a novel electrophilic reagent--β-trifluoroacetylketene diphenyldithioacetal S,S-tetroxide 3 is described. The reaction of 3 with various electron-rich aromatics such as 1,3-dimethoxybenzene, 2-methylthiophene, N-methylpyrrole, and 2-methylindole was investigated. In the course of these reactions an unusual migration of a phenylsulfonyl group takes place. An easy and ready for scale-up procedure for the synthesis of previously unknown β-aryl, α-phenylsulphonyl substituted α,β-unsaturated trifluoromethyl ketones is reported.     

One-pot synthesis of cyclic enecarbamates from lactam carbamates

A general, practical and efficient one-pot synthesis of cyclic enecarbamates is described. The protocol proceeds via reduction of lactam carbamate with Super-Hydride^®, followed by in situ dehydration with trifluoroacetic anhydride (TFAA) and diisopropylethylamine (DIPEA).     

Nucleation and growtn of polythiophene films on gold electrodes

The nucleation and growth of polythiophene films on gold electrodes has been studied using potentiostatic steps. The mechanism has been deduced and estimates made of the kinetic parameters. Dissolution of the gold substrate at potentials where thiophene polymerisation occurs is suppressed by the initial rapid formation of a monolayer of polymer. The data indicate that formation of bulk film occurs by the instantaneous nucleation and three-dimensional growth of polymer on top of this monolayer. Rate constants for growth parallel to the surface on the bare gold substrate and the covering polymer layer are surprisingly very similar. Growth perpendicular to the surface is slightly more rapid, typically by a factor of 1.5–3, although it is less dependent on potential. The high density of nuclei results in their overlap at an early stage, after which growth is only possible perpendicular to the surface. Within a narrow potential range, the observation of maxima and minima in current-time transients is interpreted in terms of the “death” and “rebirth” of growing centres.     

Elimination of the diagonalization bottleneck in parallel Direct-SCF methods

Summary It is shown that the matrix diagonalization bottleneck associated with thesequential O(N _BFN ³ ) diagonalization of the fock matrix within each iteration of the Direct-SCF procedure may be eliminated, and replaced instead with a combination ofparallel O(N _BFN ^<4 ) andsequential O(N _Sub ³ ) steps. For large basis sets, the relation N_Sub N_BFN between the dimension of the expansion subspace and the number of basis functions leads to a method of wave-function optimization in which the sequential bottleneck is eliminated. As a side benefit, the second-order iterative procedure on which this method is based displays superior convergence properties, and provides greater insight into the behavior of the energy with respect to orbital variations, than the traditional first-order, fixed-point, iterative approaches. The implementation of this method may be incorporated into essentially any existing Direct-SCF program with only minimal, and localized, changes.     

Conversion of Aldoximes into Nitriles with Raney Nickel in Refluxing 2-Propanol

Aldoximes are readily dehydrated to nitriles with Raney nickel in refluxing 2-propanol.