Methylene-azaphosphirane as a reactive intermediate

Reaction of the transient phosphinidene complexes R-P=W(CO)5 with N-substituted-diphenylketenimines leads unexpectedly to the novel 2-aminophosphindoles, as confirmed by an X-ray crystal structure determined for one of the derivatives. Experimental evidence for a methylene-azaphosphirane intermediate was found by using the iron-complexed phosphinidene iPr2N-P=Fe(CO)4, which affords the 2-aminophosphindole together with the novel methylene-2,3-dihydro-1H-benzo[1,3]azaphosphole. Analysis of the reaction pathways with DFT indicates that the initially formed methylene-azaphosphirane yields both phosphorus heterocycles by way of a [1,5]- or [1,3]-sigmatropic shift, respectively, followed by a H-shift. Strain underlies both rearrangements, which causes these remarkably selective conversions that can be tuned by changing the substituents.     

Synthesis, structures, and strain energies of dispirophosphiranes. Comparisons with dispirocyclopropanes

Six novel dispirophosphirane complexes have been synthesized from the reaction of bicycloalkylidenes with the electrophilic phosphinidene complex PhPW(CO)(5). They contain a central phosphirane ring, which is spirofused on one side to a cyclopropane or cyclobutane ring and on the other side with a three-, four-, five-, or six-membered ring. Their crystal structures and MP2/6-31G-computed geometries for simplified parent systems suggest that spirofusion with small rings results in a tightening of the central three-membered phosphaheterocycle, while spirofusion with larger rings results in a relaxation of the phosphirane geometry. Similar theoretical predictions are made for the corresponding annulated hydrocarbons. Strain energies for both the hydrocarbon and phosphorus series of structures have been calculated at G3(MP2). Whereas the [3]triangulane hydrocarbon and phospha[3]triangulane have a significant excess strain of 8.1 and 5.2 kcal/mol per spiroatom, respectively, the excess strain for systems spirofused with larger rings are negligible for the hydrocarbons and even negative for the phosphorus-containing species because of hyperconjugative stabilization.     

Dual Description of the Superconducting Phase Transition

The dual approach to the Ginzburg-Landau theory of a Bardeen-Cooper-Schrieffer superconductor is reviewed. The dual theory describes a grand canonical ensemble of fluctuating closed magnetic vortices, of arbitrary length and shape, which interact with a massive vector field representing the local magnetic induction. When the critical temperature is approached from below, the magnetic vortices proliferate. This is signaled by the disorder field, which describes the loop gas, developing a non-zero expectation value in the normal conducting phase. It therby breaks a global U(1) symmetry. The ensuing Goldstone field is the magnetic scalar potential. The superconducting-to-normal phase transition is studied by applying renormalization group theory to the dual formulation. In the regime of a second-order transition, the critical exponents are given by those of a superfluid with a reversed temperature axis.     

Bidentate phosphorus baskets by intramolecular phosphinidene addition

Intramolecular phosphinidene addition to the C==C bond of Mo-complexed, seven-membered phosphorus heterocycles affords three novel [(diphos)Mo(CO)(4)] complexes (18-20). The three bidentate phosphorus baskets differ in the composition of the seven-membered ring: one of the phosphorus atoms is flanked by CH(2), NCH(3), or O. The unsaturated tetrahydrophosphepine precursors are synthesized by either ring-closing metathesis (C and N derivatives) or by a cyclization sequence (O derivative). The crystal structures of the nitrogen- (19) and oxygen-containing (20) baskets have relatively small P-Mo-P angles of 76.240(13) degrees and 77.626(12) degrees , respectively, and complex 20 has slightly shortened Mo--P bond lengths.     

Seismoelectric Fluid/Porous-Medium Interface Response Model and Measurements

Coupled seismic and electromagnetic (EM) wave effects in fluid-saturated porous media are measured since decades. However, direct comparisons between theoretical seismoelectric wavefields and measurements are scarce. A seismoelectric full-waveform numerical model is developed, which predicts both the fluid pressure and the electric wavefields in a fluid in which a porous disc is embedded. An experimental setup, in which pressure and electric signals in the fluid are simultaneously measured, is presented. The setup allows the detection of the EM field that is generated when an acoustic wave crosses the interface between the fluid and the thin porous disc, without interference of electrical fields that are present within seismic body waves. The predicted pressure wavefield agrees well with the measurements in terms of acoustic wave travel times, waveforms, and amplitudes. The electric wavefield predictions agree with the recordings in terms of travel times, waveforms, and spatial amplitude decay. A discrepancy in amplitude of the converted EM signal is observed. Theoretical amplitudes that are smaller than the measurements were also reported in previous literature. These results seem to validate seismoelectric theory.