Synthesis and characterization of triphenylmethylphosphonium transition metal salts

Triphenylmethylphosphonium salts, [PPh3Me]aMXn (M=Cu2+, Co2+, Mn2+, Ni2+ Fe3+ Pb2+ and Hg2+; X=Cl or I; a=1 or 2 and n=3 or 4) prepared by reacting PPh3MeX with the metal dihalide in EtOH sol-utions, have been characterized by electronic, Raman, far i.r. and Mo¨ssbaur spectra and by their magnetic properties as well as by elemental analyses. The copper complexes [PPh3Me]2CuCl4 and [PPh3Me]2Cu3Cl8 were characterized by X-ray crystallography and the structures are described. Powder diffraction patterns have shown that the cobalt and manganese tetrachloride complexes are isomorphous. Investigation by d.s.c. measurements showed that the complexes exhibit structural phase transitions.     

A convenient synthesis of 1-methyl-4-oxopiṕecolic acid methyl ester

An efficient and convenient synthesis of the title compond 1 is described. The approach to the synthesis is based on hydride reduction of the 4-methoxypyridinium salt 5 , followed by acid hydrolysis of the resulting vinyl ether intermediate 6 .     

Second order non-linear equations of motion for spinning highly flexible line elements

The second order non-linear equations of motion are formulated for spinning line elements having little or no intrinsic structural stiffness. The derivation is based on the extended Hamilton's principle and includes the effect of initial geometric imperfections (axial, curvature, and twist) on the line element dynamics. For comparison with previous work, the non-linear equations are reduced to a linearized form frequently found in the literature. The comparison revealed several new spin-stiffening terms that have not been previously identified and/or retained. They combine geometric imperfections, rotary inertia, Coriolis, and gyroscopic terms.     

Dichlorphosphatokomplexe der Nitridchloride von Molybdän und Wolfram

Dichlorophosphate Complexes of the Nitrido Chlorides of Molybdenum and Tungsten Tetraphenylarsonium dichlorophosphate AsPh₄[PO₂Cl₂], is prepared by the reaction of AsPh₄Cl with P₂O₃Cl₄. The vibrational spectrum is reported as well as the valence force constants of the [PO₂Cl₂]^? ion. The f-values are clearly smaller than those of the isoelectronic SO₂Cl₂ molecule. The dichlorophosphate ion forms complexes with the nitride chlorides MNCl₃ (M ? Mo, W) of the type [MNCl₃(PO₂Cl₂)]₂^2?, which are characterized by their i.r. spectra.     

Coordination compounds of hydrazine derivatives with transition metals. Part 27. Coordination chemistry of 4-amino-3-alkyl-5-thio-1,2,4-triazolines and 4-amino-5-oxo-3-thioxo-6-alkyl-2,3,4,5-tetrahydro-1,2,4-triazines

Summary Mono-, bis- and tris-ligand nickel(II) and cobalt(II) complexes with 4 amino-3-alkyl-5-thio-1,2,4-triazolines (HRL) (R=H, Me, or Et) and 4-amino-5-oxo-3-thioxo-6-methyl-2,3,4,5-tetrahydro-1,2,4-triazine (HL') have been prepared and characterized. In these complexes both HRL and HL' are in the neutral thione form. Nickel(II) and cobalt(II) complexes with mononegative thiolate ligands have been also isolated.The reaction of HL' with copper(II) salts in a molar ration of 11 results in the formation of [Cu(HL')X] (X=Cl or Br) and Cu(L')X (X=NO₃ or CH₃COO). However, in the presence of a large excess of HL' the reaction proceeds with partial reduction of Cu^II and both [Cu(HL')X₂] and [Cu(HL')₂]X have been isolated and characterized. The mechanism of copper(II) reduction by HL' is discussed.     

Eine neue und unerwartete Form des Dodecaiodid-Ions I122–: Darstellung und Kristallstruktur des Bis[kalium(dibenzo-18-krone-6)]dodecaiodids [K(C20H24O6)]2I12

Studies of Polyhalides. 32. A New and Unforeseen Shape of the Dodecaiodide Ion I₁₂^2–: Preparation and Crystal Structure of Bis[potassium(dibenzo-18-crown-6)]dodecaiodide [K(C₂₀H₂₄O₆)]₂I₁₂ Particularly iodine rich polyiodides tend to form extended iodine nets by multiply concatenating iodide or triiodide ions through iodine molecules. Therefore the discovery of a not ramified, nearly isolated dodecaiodide ion I₁₂^2– in the new compound [K(C₂₀H₂₄O₆)]₂I₁₂ seems to be unexpected. This ion may be described as an extraordinary long fragment of the triiodide-iodine chain (I₃^– · I₂)_∞.     

Effect of working temperature on young's modulus of electrolytic copper

Electrolytic copper wires of different grain diameters were given variable amounts of plastic strain, and then subjected to increased tensile loadings at different working temperatures. The associated changes in Y. M. were measured. Plastic strain decreased Y. M. at first to a minimum value, then it increased Y. M. This effect was interpreted in terms of texture variations and mutual dislocation interactions. Increasing working temperature decreased Y. M. because of accompanying increase in slip distances.