Temperature dependence of kinetics of triplet formation in phenazine: analysis by analogue computer

The temperature dependence of kinetic parameters of triplet phenazine have been determined by analysis of transient response to photoexcitation. The analogue computer used in the analysis is described.     

Transient nutations of photoelectrons from alkali metal anions

Transient nutations of the magnetization of photoelectrons ejected from rubidium and cesium anions are described. The nature of the nutations requires that the time between photoexcitation and appearance of the photoelectron is less than ≈10^?7 s.     

Efficient and facile Ar-Si bond cleavage by montmorillonite KSF: synthetic and mechanistic aspects of solvent-free protodesilylation studied by solution and solid-state MAS NMR

A facile and efficient method for the cleavage of the Ar-Si bond of various aryl trimethyl silanes is described. When adsorbed on montmorillonite KSF (mont KSF), these arylsilanes readily undergo a solvent-free protodesilylation to the corresponding arenes at room temperature in excellent yields. This approach seems to be superior to the traditional mild methods (i.e., desilylation by TFA, TBAF, CsF), in terms of reaction yield, rate, and environmentally benign conditions. Some mechanistic studies using both solution and solid-state magic-angle spinning (SS MAS) (1)H NMR are also presented.     

Palladium complexes of perylene diimides: strong fluorescence despite direct attachment of late transition metals to organic dyes

We prepared the first sigma-bonded metal complexes of widely utilized organic dyes, perylene tetracarboxylic acid diimides (PDIs). These 1,7-dipalladium PDI complexes were synthesized by C-Br oxidative addition of 1,7-dibromo-N,N'-dicyclohexyl PDI (Br2PDI) to Pd(0) phosphine complexes bearing triphenylphosphine and bischelating 1,2-bis(diphenylphosphino)ethane (dppe). The structures of Pd-PDI complexes were elucidated by single-crystal X-ray analysis. Surprisingly, despite direct attachement of two late transition metal centers, Pd-PDI systems are highly fluorescent (Phi=0.65 and 0.22 for triphenylphosphine and dppe systems, respectively). This is rationalized in terms of weak electronic interactions between the metal centers and PDI pi-system, as revealed by TD-DFT calculations.     

SYNTHESIS OF THE 8-PHOSPHABICYCLO[3.2.1]OCTA-2,6-DIENE RING SYSTEM

Abstract

The 8-phosphabicyclo[3.2.1]octa-2,6-diene ring system is conveniently synthesized by the addition of chloro(diisopropylamino)phosphenium ion ((Cl)(i-Pr₂N)P⁺,1) to cycloheptatriene. Hydrolysis of the primary adduct yields the corresponding phosphinamide (3). The NMR of 3 is discussed in terms of its structure, and the orientation at P is assigned by a combination of 2-D NMR techniques. The structure of 3 is also probed by model calculations at the MNDO level.     

A Mo(VI) alkylidyne complex with polyhedral oligomeric silsesquioxane ligands: homogeneous analogue of a silica-supported alkyne metathesis catalyst

A highly active alkyne metathesis catalyst is realized by replacing the amide ligands of a molybdenum(VI) trisamide alkylidyne complex with silanol groups from incompletely condensed POSS (polyhedral oligomeric silsesquioxane) ligands. This catalyst serves as an effective homogeneous mimic of an amorphous silica-supported catalyst. Reactivities of various catalytic mixtures are reported along with an X-ray structure of the aniline-coordinated amidodisiloxymolybdenum(VI) alkylidyne complex.     

Pretubulysin,a Potent and Chemically Accessible Tubulysin Precursor from Angiococcus disciformis

Simplify, simplify, simplify! Pretubulysin (structure without the green substituents), a simplified tubulysin was prepared in the laboratory and also found in a natural myxobacterial source. This biosynthetic precursor of the tubulysins is not as active as tubulysins A and D but is still effective in picomolar concentrations against cancer cell lines.

     

Magnetic moments of mirror nuclei with tilted-foil polarization

We report here on an ongoing experimental program initiated at the ISOLDE facility at CERN for the measurement of magnetic moments of short-lived radionuclides, with the emphasis on magnetic moments of mirror nuclei in far-from-stability regions. The nuclei are polarized by the tilted foil technique and the resulting 0–180^○ βasymmetry is monitored as a function of rf frequency applied in an NMR setup. In order to achieve sufficiently high energy for transmission through the foils, the experimental setup is mounted on a high voltage platform. The first experiment in this program was the measurement of the βasymmetry and the NMR resonance for the ground state of ²³Mg (I=3/2, T_1/2=11.3 s), yielding μ=−0.533(6) nm. Improvements to the experimental setup are presently being designed, to be used in conjunction with the new developments at ISOLDE for obtaining high charge-state ions from the EBIS (REX-ISOLDE) ion source. This will help pave the way for measurements of magnetic moments of T=3/2 nuclei in the s–d shell and of T=1/2 f-shell nuclei. The study of relaxation times and other solid-state phenomena in semiconductors and other materials of interest using this technique is also contemplated. This revised version was published online in July 2006 with corrections to the Cover Date.