Reactions of N-silylphosphoranimines with alcohols: synthesis and structure of cyclotriphosphazenes with nongeminal methyl and phenyl substituents

The reactions of Me(3)SiN=P(OR")RR'(R" = Ph, CH(2)CF(3); R, R' = Me, Ph) with alcohols were investigated. With nonequivalent amounts of CF(3)CH(2)OH, the reactions produced high yields of the cyclic phosphazene (Me(2)PN)(3) and both the cis and trans isomers of nongeminally substituted [(Ph)(Me)PN](3). The isomers of this new cyclic phosphazene were separated by column chromatography and characterized by NMR and IR spectroscopy, elemental analysis, and X-ray crystallography. Crystals of the cis isomer 6a have a monoclinic crystal system, while the trans isomer 6b has a triclinic crystal system with two different molecules in an asymmetric unit. The bond lengths and bond angles are very similar to those of the simpler cyclic trimers (Me(2)PN)(3) and (Ph(2)PN)(3.) A likely pathway for the formation of these compounds is discussed.     

NEW CYCLIC AND POLYMERIC PHOSPHAZENES DERIVED FROM N-SILYLPHOSPHORANIMINES

Silicon-nitrogen-phosphorus compounds of the type Me ₃ SiN═PR(R′)X(X= Cl, Br, OCH₂CF ₃ , OPh), known as N-silylphosphoranimines,are useful precursors to both cyclic and polymeric phosphazenes.Depending on the leaving group (X), thermolysis reactions afford either cyclic trimers, [N═PR(R′)] ₃ (when X = Cl, Br), or linear polymers,[N═PR(R′)]_n (when X = OCH ₂ CF ₃ or OPh). Treatment of the P-trifluoroethoxy and P-phenoxy derivatives, Me ₃ SiN═PR(R′)X (X = OCH ₂ CF ₃ , OPh), with alcohols at lower temperature usually results in the formation of cyclic phosphazene trimers via silyl ether elimination. Recently, we have applied these synthetic methods to the preparation of some new phosphazene systems including a series of 4-aryl-functionalized trimers and polymers and a variety of non-geminal, mixed-substituent cyclic trimers. Representative examples of the synthesis, structural characterization, and reactivity of these new phosphazenes and their Si─N─P precursors are reported here.     

High precision measurement of the superallowed 0+ --> 0+ beta decay of 22Mg

The half-life, 3.8755(12) s, and superallowed branching ratio, 0.5315(12), for 22Mg beta decay have been measured with high precision. The latter depended on gamma-ray intensities being measured with an HPGe detector calibrated for relative efficiencies to an unprecedented 0.15%. Previous precise measurements of 0+ --> 0+ transitions have been restricted to the nine that populate stable daughter nuclei. No more such cases exist, and any improvement in a critical Cabibbo-Kobayashi-Maskawa unitarity test must depend on precise measurements of more exotic nuclei. With this branching-ratio measurement, we show those to be possible for T(z)=-1 parents. We obtain a corrected Ft value of 3071(9) s, in good agreement with expectations.     

Outer space formation of a laser host glass

Classical crystallization calculations were performed to determine the possibility of forming a particular type of laser glass with the avoidance of devitrification in an outer space laboratory. Although the laser glass in question readily crystallizes in an earth environment, it is demonstrated that under the homogeneous nucleating conditions obtainable in a zero gravity laboratory this laser glass may be easily quenched to a virtually crystal-free product. Use of this material as a host in a neodymium glass laser would result in a more than 10% increase in efficiency when compared to laser glass rods of similar composition currently commercially available.     

Condition Monitoring of Ground Anchorages by Dynamic Impulses: GRANIT System

The GRANIT system operates by applying an impulse of known force by means of an impact device that is attached to the tendon of the anchorage. The vibration response signals resulting from this impulse are complex in nature and require analysis to be undertaken in order to extract information from the vibrational response signatures that is relevant to the condition of the anchorage. In the system, the complicated relationship that exists between characteristics of an anchorage and its response to an impulse is identified and learned by a novel artificial intelligence network based on artificial intelligence techniques.The results presented in this paper demonstrate the potential of the GRANIT system to diagnose the integrity of ground anchorages at a site near Stone, England, by using a trained neural network capable of diagnosing the post-tension level of the anchorage. This neural network was used for the diagnosis of load in a second ground anchorage adjacent to the original anchorage used for the training of the neural network. Further tests were taken with a different anchor head configuration of the anchorage and a different relationship between the signature response of the anchorage to an applied impulse and its post-tension level was found.Problems encountered during the diagnosis of this second set of test signatures by the trained neural network are investigated with the use of a lumped parameter dynamic model. This model is able to identify the parameters in the anchorage system that affect this change in response signature. The results from the investigation lead to a new form of classification for the installed anchorages, based on their anchor head configuration.Laboratory strand anchorage tests were undertaken in order to compare with and validate the results obtained from the field tests and the lumped parameter dynamic model.     

Tuning of the spin distribution between ligand- and metal-based spin: electron paramagnetic resonance of mixed-ligand molybdenum tris(dithiolene) complex anions

Electron paramagnetic resonance spectra of homoleptic and mixed-ligand molybdenum tris(dithiolene) complex anions [Mo(tfd)(m)(bdt)(n)](-) (n + m = 3; bdt = S(2)C(6)H(4); tfd = S(2)C(2)(CF(3))(2)) reveal that the spin density has mixed metal-ligand character with more ligand-based spin for [Mo(tfd)(3)](-) and a higher degree of metal-based spin for [Mo(bdt)(3)](-): the magnitude of the isotropic (95,97)Mo hyperfine interaction increases continuously, by a factor of 2.5, on going from the former to the latter. The mixed complexes fall in between, and the metal character of the spin increases with the bdt content. The experiments were corroborated by density functional theory computations, which reproduce this steady increase in metal-based character.     

Universal features of terahertz absorption in disordered materials

Using an analytical theory, experimental terahertz time-domain spectroscopy data, and numerical evidence, we demonstrate that the frequency dependence of the absorption coupling coefficient between far-infrared photons and atomic vibrations in disordered materials has the universal functional form, C(omega)=A+Bomega(2), where the material-specific constants A and B are related to the distributions of fluctuating charges obeying global and local charge neutrality, respectively.