An efficient synthesis of acetylide/trimetal/acetylide molecular wires

Efficient syntheses are reported for incorporating trimetal units of the type M(3)(dpa)(4)(2+) (M = Cr, Co, Ni, and dpa = 2,2'-dipyridylamide) into polyalkynyl assemblies to give the prototypical bis-phenylacetylide complexes M(3)(dpa)(4)(CCPh)(2). Reactions of M(3)(dpa)(4)Cl(2) with LiCCPh have led only to mixtures of products which cocrystallize forming materials of the composition M(3)(dpa)(4)(CCPh)(x)()Cl(2)(-)(x)(). Here we report that acetonitrile complexes [M(3)(dpa)(4)(NCCH(3))(2)](PF(6))(2) react cleanly with LiCCPh in MeCN to afford the desired target molecules in 40-60% yield and in excellent purity. Isolation of the mixed ligand complex [Co(3)(dpa)(4)(NCCH(3))(CCPh)]PF(6) has been accomplished, which suggests that these reactions are stepwise and that it will be possible to synthesize mixed acetylide complexes (i.e., M(3)(dpa)(4)(CCR)(CCR')) via this method.     

Photosensitized dehydrochlorination of poly(vinyl chloride). III. Reaction of thermally degraded poly(vinyl chloride) with hydrogen chloride

Films prepared from thermally degraded poly(vinyl chloride) were photolyzed in the presence of hydrogen chloride. When the light was filtered through a Pyrex disk, the absorbance in the region between 270 nm and about 415 nm decreased and reached a minimum value but the absorbance increased at wavelengths shorter than 270 nm and longer than 415 nm. Maximum bleaching occurred at a wavelength which depended on that of the irradiating light. When the Pyrex filter was omitted, an additional slower photodehydrochlorination reaction was superimposed on the photobleaching reaction. Photolysis of hexane or ethanol solutions of 1,8-diphenyloctatetra-1,3,5,7-ene and hydrogen chloride showed a similar reaction involving bleaching of the absorption of the polyene structure. The problems of using absorbance as an indication of the extent of the photodegradation of poly(vinyl chloride) are discussed.     

Detection of unexploded ordnance by PGNAA based borehole-logging

The performance of a borehole-logging system, based on prompt-gamma-neutron-activation-analysis (PGNAA), for explosive detection was studied by Monte-Carlo simulations. The prompt gamma of nitrogen, which is a constituent of common explosive, was used to identify the unexploded ordnance (UXO). Our results show that the minimum counting time depends on the soil moisture, the cladding thickness and the explosive composition. In conjunction with the standard detection by magnetometry, the PGNAA is a promising analytical technique for definitive identification of deep buried UXOs.     

Pushing and pulling electrons: the effect on the heat of formation of trifluoromethyl compounds

The effect on heats of formation, of conjoined or proximate functional groups which can interact via polar or resonance effects, is examined using the –CF₃ group as a standard. Two metrics are applied: the difference in heat of formation of G–CF₃ and G–CH₃, where –G is a wide range of functional groups, and also the deviation of the heat of formation of G–CF₃ from the average of the heats of formation of G–G and CF₃–CF₃. This latter metric reveals both stabilizing and destabilizing effects on the heat of formation, of up to 60 kcal/mol, depending on the polar and resonance nature of the –G structure. The possibility of using such metrics as a correction the group additivity values is examined.     

Regiospecific synthesis of cepanolide,a cancer chemoprotective micronutrient found in green onions

The naturally occurring γ-hydroxy-β-sulfanylbutenolide cepanolide and a range of new analogues were synthesized in concise, regiospecific manner through the combined use of 2-silyloxyfuran oxyfunctionalization and tandem thio-Michael addition/elimination.     

The millimeter-wave spectrum of acetaldehyde in its two lowest torsional states

A large number of new millimeter-wave spectral lines of gaseous acetaldehyde have been measured at frequencies up to 250 GHz. These lines arise from rotational transitions of acetaldehyde in its two lowest (v_t = 0,1) torsional states and involve angular momentum quantum numbers J ≤ 12 and K ≤ 10. A global data set consisting of 562 lines has been obtained by combining the millimeter-wave lines with previously measured lower frequency data involving the two lowest torsional states. This data set has been analyzed via an internal axis method previously used to study the spectra of CH₃OH and CH₃SH. The root-mean-square deviation of the fit is only 685 kHz. An analogous least-squares fit to 335v_t = 0 lines yields a root-mean-square deviation of 269 kHz.     

The generic condition is generic

We consider the generic condition for vectors—both null and non-null—at a fixed pointp of a spacetime, and ask just how generic this condition is. In a general spacetime, if the curvature is not zero at the pointp, then the generic condition is found to be generic in the mathematical sense that it holds on an open dense set of vectors atp; more specifically, if there are as many as five non-null vectors in general position atp which fail to satisfy the generic condition, then the curvature vanishes atp. If the Riemann tensor is restricted to special forms, then stronger statements hold: An Einstein spacetime with three linearly independent nongeneric timelike vectors atp is flat atp. A Petrov type D spacetime may not have any nongeneric timelike vectors except possibly those lying in the plane of the two principal null directions; if any of the non-null vectors in such a plane are nongeneric, then so are all the vectors of that plane, as well as the plane orthogonal to it.