Reaction des lithiens avec les organophosphores. Reaction d'addition du t-butyllithium sur le noyau benzenique des sels de phenylphosphoniums

A new reaction of organolithium compounds with phosphonium salts is described; reaction of t-butyllithium with dibenzylaminophosphonium or tetraphenylphosphonium bromides takes place through addition of the t-butyl group on a benzene ring at the position para to the phosphorus atom, the ylid formed reacts in a characteristic Wittig reaction with p-tolylaldehyde.     

Hydrogen abstraction and dimerisation reactions of some organo-transition metal free radicals

The 17-electron species [M(CO)_5χL_χ] (M  Mn, Re, χ  0; M  Mn, Re; L  Ph₃P, χ  1, 2; M  Mn, Re; L  (o-MeC₆H₄O)₃P, χ  2; M  Mn; L  (p-ClC₆H₄O)₃P, (PhO)₃P, χ  2; M  Mn; L  P(OMe)₃, χ  3) have been generated by one electron oxidation of the corresponding anions and show typical radical reactivity, undergoing dimerisation or hydride abstraction in reactions controlled by steric effects. Evidence is presented for the source of the hydrogen atom. The 19-electron species [M(CO)₃(η⁷-C₇H₇)]^? (M  Cr, Mo) and [Fe(CO)₃(η⁵-C₆H₇)]^?, generated by reduction of the corresponding cations, undergo dimerisation at the organic ligand. Similar treatment of [Fe(CO)₂-L(η-cp)]⁺ (L  CO, PPh₃, P(OPh)₃, Me₂CO) yields [Fe₂(CO)₄(η-cp)₂] and these reduction reactions are rationalised in terms of the nature of the HOMO in the intermediate radical. Similar reduction of [Rh(diphos)₂]⁺ yield the 17-electron intermediate [Rh(diphos)₂] and this also undergoes hydrogen abstraction.     

Stabilization of platinum(II) hydrides by tri-t-butylarsine; facile syntheses of stable trans-PtH2[As(t-Bu)3]2 and trans-PtHX[As(t-Bu)3]2 complexes

trans-PtH₂[As(t-Bu)₃]₂ was prepared in very good yield by afacile reaction of K₂PtC1₄ with As(t-Bu)₃ in alkaline ethanol. Treatment of trans-PtH₂[As(t-Bu)₃]₂ with CF₃CO₂H or HCI afforded trans-PtH(O₂CCF₃)[As(t-Bu)₃]₂ or trans-PtHCl[As(t-Bu)₃]₂. respectively, in almost quantitative yield.     

Solvent effects on the syn-anti isomerization rates of hydrazones of acetone

The coalescence temperature for the C-methyl peaks in the NMR spectra of hydrazones of acetone are above 200°, indicating an energy barrier for syn-anti isomerization greater than 28 kcal mole^?1. the presence of halogenated compounds decreases the energy barrier, due to the formation of a charge transfer complex between the hydrazone acting as a donor and the halogenated compound acting as the electron acceptor.     

The reaction of amines with phthalimide derivatives a convenient synthesis of isoxazolidine

The reaction of tert-butylamine, isoxazolidine and hydrazine with N-[(3-chloropropyl)oxy]phthalimide is investigated. A convenient synthesis of oxazolidine is described.     

The phase diagram for the binary system K2CrO4CaCrO4

The phase diagram for the binary system K₂CrO₄CaCrO₄ has been determined for CaCrO₄ concentrations up to 60 mole%, using the techniques of differential thermal analysis, X-ray diffraction, and drop calorimetry. Essential features of the phase diagram are: the solid-solid phase transition for pure K₂CrO₄ at 670°C, β-K₂CrO₄ ? α-K₂CrO₄; a eutectoid reaction at 14 mole% CaCrO₄ and 548°C, β-K₂CrO₄ ? α-K₂CrO₄ + K₂CrO₄ · CaCrO₄; a peritectoid event at 50 mole% CaCrO₄ and 640°C, β-K₂CrO₄ + CaCrO₄ ? K₂CrO₄ · CaCrO₄; and a eutectic reaction at 51 mole% CaCrO₄ and 678°C, L ? β-K₂CrO₄ + CaCrO₄. X-ray diffraction studies lead to the determination of the unit cell dimensions for the K₂CrO₄ · CaCrO₄ double salt, a C-centered monoclinic form with a₀ = 7.615(6) Å, b₀ = 22.797(15) Å, c₀ = 9.777(9) Å, β = 115.45(5)°.     

Enantiomers of polarized alkenes: chromatographic enrichment and thermal interconversion

(+)- and (?)-$\text{1}$ as well as (+)- and (?)-$\text{2}$ were partially separated by liquid chromatography on triacetylcellulose; racemizations resulted in the barriers (Table 2) to rotation via planarized transition states.     

The crystal structure of CuVo3(II), a high-pressure ilmenite phase

The crystal structure of a second high-pressure copper vanadate phase, CuVO₃(II), has been determined and refined by full-matrix least-squares procedures using automatic diffractometer data to a residual R = 0.042 (R_w = 0.051). The space group is rhombohedral, $\text{R}\text{3}$, with hexagonal unit cell a = 4.966(2) and c = 14.084(5) Å [a_R = 5.501(2) Å and α = 53.66(3)°]. The structure is the fully ordered ilmenite-type and, on the basis of published magnetic data and the interatomic distances, the valence distribution Cu⁺V⁵⁺O₃ is proposed. This represents a unique example of Cu⁺ in an octahedral environment.     

Heat transfer from a rarefied plasma flow to a metallic or nonmetallic particle

Heat transfer from a plasma flow to a metallic or nonmetallic spherical particle is studied in this paper for the extreme case of free-molecule flow regime. Analytical expressions are derived for the heat flux due to, respectively, atoms, ions, and electrons and for the floating potential on the sphere exposed to a two-temperature plasma flow. It has been shown that the local or average heat flux density over the whole sphere is independent of the sphere radius and approximately in direct proportion to the gas pressure. The presence of a macroscopic relative velocity between the plasma and the sphere causes substantially nonuniform distributions of the local heat flux and enhances the total heat flux to the sphere. The heat flux is also enhanced by the gas ionization. Appreciable difference between metallic and nonmetallic spheres is found in the distributions along the oncoming flow direction of the floating potential and of the local heat flux densities due to ions and electrons. The total heat flux to the whole sphere is, however, almost the same for these different spheres. For a fixed value of the electron temperature, the heat flux decreases with increasing temperature ratio T_e/T_h.     

Electrical,magnetic, and EPR studies of the quaternary chalcogenides Cu2AIIBIVX4 prepared by iodine transport

Electrical, magnetic, and electron paramagnetic resonance (EPR) measurements have been made on crystals and powders of several quaternary chalcogenides of the type Cu₂A^IIB^IVX₄, where A^II = Zn, Mn, Fe, or Co, B^IV = Si, Ge, or Sn, and X = S or Se. The electrical properties of these compounds are extrinsic, but their magnetic properties do not appear to be affected by impurities. The magnetic moments of the Cu₂MnBX₄ compounds decrease with increasing covalency of the MnX bond, and those of Cu₂FeGeS₄ and Cu₂CoGeS₄ reflect an orbital contribution to the moment. Both the Weiss constants and magnetic ordering temperatures in these compounds show an evolution from antiferromagnetism to ferromagnetism with increasing separation between the moments. Magnetic measurements on single crystals of Cu₂MnGeS₄, Cu₂CoGeS₄, and Cu₂FeGeS₄ indicate that only the latter is anisotropic. EPR measurements on crystals and powders of Cu₂ZnGeS₄ doped nominally with 0.1% Mn reveal that Mn²⁺ experiences an axial distortion and that the bond ionicity is the same as in ZnS.