Synthesis and properties of alkyldicyclopentadienyl-vanadium(III) compounds

The compounds Cp₂VR (R = CH₃, C₂H₅, n-C₃H₇, n-C₄H₉, n-C₅H₁₁, CH₂C(CH₃)₃ or CH₂Si(CH₃)₃) have been prepared from Cp₂ VCl and RMgX in n-pentane. The air-sensitive compounds are stable at room temperature, but decompose between 65 and 138°C. The thermal stability decreases in the order R = CH₃ CH₂Si(CH₃)₃ > C₂H₅ > CH₂C(CH₃)₃ > n-C₅H₁₁ > n-C₄H₉ > n-C₃H₇. Compounds with R = i-C₃H₇ or t-C₄H₉ could not be obtained.     

The crystal and molecular structure of 1,1,1,3,3,3-hexaphenyl-1,3-disilapropane

Crystals of the title compound H₂C(SiPh₃)₂ are triclinic, space group P$\text{1}$, with a = 9.290(2), b = 12.128(4), c = 16.882(4) Å, α = 62.08(1), β = 106.88(1), γ = 117.28(2)° and Z = 2. The central skeletal angle SiCSi is 128.8(7)°. The structures of the molecules H₂C(SiR₃)₂ (R = H, CH₃, and Ph) are compared and discussed: a simple model for the skeletal geometry of species H₂C(MR₃)₂ is proposed, and tested against experimental data and theoretical calculations.     

Conformations in the tetrahydropyran-2-one ring

Force-field calculations in combination with ¹H NMR spectroscopy, IR data and X-rays diffraction unambiguously delineate the conformational properties of tetrahydropyran-2-one derivatives which exhibit psychostimulant and antidepressive activity.     

Dehydrochlorination of monodisperse poly(vinylidene chloride) latex

The objective of the work described in this paper was to produce dispersions of small spherical carbon particles, having particle diameters in the region of 0.1 μm. To this end, the dehydrochlorination of poly(vinylidene chloride) (PVDC) latex particles was attempted. The PVDC latex was prepared by a dispersion polymerization route. Both chemical and thermal dehydrochlorination routes were attempted. Chemical dehydrochlorination, using a variety of base/solvent systems, led to nonporous, spherical black particles of the required size, but which contained only 60% carbon; most of the remainder was oxygen, introduced by nucleophilic substitution reactions. Thermal dehydrochlorination, at 700°C under a nitrogen atmosphere, using a fluidized bed arrangement, on the other hand, led to black particles, having 90% carbon and which retained their sphericity, but which were highly porous. Initial chemical dehydrochlorination, prior to thermal treatment, did not seem to reduce the porosity of the final carbons. Dispersions of the carbon particles in a variety of solvents were readily achieved.     

The transparency of polyurethane-poly(methyl methacrylate) interpenetrating and semi-interpenetrating polymer networks

Various combinations of polyurethane (PUR) and poly(methyl methacrylate) (PMMA) were prepared as interpenetrating polymer networks (IPN) or semi-IPNs. In the latter, either the PUR or the PMMA component was crosslinked. The optical transmissions of these materials were measured as a function of the crosslink degrees of both phases. The role of the PUR chain extender, poly(oxypropylene) glycol, is discussed. It is concluded that any means which increases the degree of phase dispersion favours the transparency of PUR/PMMA based IPNs and semi-IPNs.     

The effect of a magnetic field on the singlet/triplet ratio in geminate ion recombination

Excited state formation by ion recombination in solutions of fluorene in squalene has been studied by pulse radiolysis at the center of a large electromagnet. The products of the slower part of the ion recombination are affected by an applied magnetic field. The fluorescence yield increases by a factor of about 1.5 whereas the triplet yield decreases.     

Crystallographic parameters in α-UF5 and U2F9 by multiphase refinement of high-resolution neutron powder data

The crystal structures of α-UF₅ and U₂F₉ were refined with high-resolution neutron powder diffraction data from an $\text{α-}\text{UF}{}_5\text{U}{}_2\text{F}{}_9$ mixture. Refinement was achieved by a multiphase Rietveld profile refinement technique. The results are compared with previous X-ray and neutron powder studies.     

Oxidation of the [Rh(CO)2Cl2] anion in aqueous solution

The reaction of rhodium(I) carbonyl chloride, [Rh(CO)₂Cl]₂, with dichromate, cerium(IV) sulfate, hexachloroplatinic acid or p-benzoquinone in aqueous hydrochloric acid proceeds by consumption of 4 equivalents of oxidizing agent per mole or rhodium(I) in accordance with the equation Rh^I(CO)₂  4e + H₂O → Rh^III(CO) + 2H⁺ + CO₂A “cyclic” oxidation mechanism is suggested.     

Electrophilic reactions of chlorin derivatives and a comprehensive collection of 13c data of these products and closely related compounds

Vilsmeier-formylation of the copper(II) complex of chlorin-e₆ trimethyl ester (2), under mild conditions, gives selective substitution in the 3-vinyl group. In contrast chlorination of 2 is shown to lead to selective substitution at position 20 of the macrocycle. A similar result is found for [3-ethyl]-isochlorin-e₄ dimethyl ester (17) although further reaction leads to more highly chlorinated products which have been isolated and identified. ¹³C NMR data for some of these compounds and several related chlorin derivatives are reported. In particular, after correction of the literature, many of the quaternary carbon signals of the macrocycle are assigned and substituent effects assessed. Consideration of the shifts of the α-pyrrolic carbons confirms that chlorin and its derivatives exist in a tautomeric form with the two inner H atoms on diagonally opposite pyrrole rings A and C. Such a form allows a satisfactory explanation of the substituent chemical shifts of the formyl group at positions 15 and 20 to be made.