Synthesis, characterization, and substitution chemistry of [Bu4N]2[W6Cl8(OSO2CF3)6]. A versatile precursor for axially substituted clusters containing the (W6Cl8)4+ core

The new cluster [Bu4N]2[W6Cl8(OSO2CF3)6] (1) has been prepared and structurally characterized. This material is an effective precursor for the generation of cluster ions with the general formula [W6C18L6]n (L = Cl-, Br-, I-, NCS-, NCO-, NCSe-, and O=PPh3; n = 2- or 4+). The last three clusters are new. The products have been characterized by IR spectroscopy, NMR spectroscopy, and FAB mass spectrometry. In addition to 1, the products [Bu4N]2[W6C18(NCS)6] (5) and [Bu4N]2[W6C18(NCO)6] (7) were structurally characterized. Crystal data for 1: space group, P2(1/c) (No. 14); a = 11.116(5) A; b = 27.952(1) A; c = 24.516(1) A; beta = 95.182(9) degrees; V = 7586.3(5) A3; Z = 4. Crystal data for 5: space group, P2(1/n) (No. 14); a = 11.3323(9) A; b = 12.3404(9) A; c = 44.583(3) A; beta = 97.089(1) degrees ; V = 6187.1(7) A3; Z = 4. Crystal data for 7: space group, P1 (No. 2); a = 11.8009(8) A; b = 11.9332(8) A; c = 11.9522(8) A; alpha = 77.904(1) degrees; beta = 95.182(9) degrees; gamma = 62.574(1) degrees V = 1450.5(2) A3; Z = 1.     

Vibrational spectroscopy and structure of polymer electrolytes,poly(ethylene oxide) complexes of alkali metal salts

Complexes of poly(ethylene oxide) (PEO), with various alkali metal salts are known to exhibit ionic conductivities which exceed 10^?5(Ωcm)^?1 at moderate temperatures. We have employed IR and Raman spectroseopy to study well characterized samples of the following polymer-salt complexes: PEO·NaBr, PEO·NaI, PEO·NaSCN, PEO·NaBF₄, PEO·NaCF₃SO₃, PEO·KSCN, PEO·RbSCN and PEO·CsSCN. Cation-dependent vibrational bands observed in the far IR and M-O_n symmetric stretching bands observed in the Raman support a cation-oxygen atom interaction, and indicate the polyether chain may wrap around the cations. In particular, NaX and KX complexes of PEO are believed to have a helical configuration for the polymer which differs from that of pure PEO. Some general rules are presented for polymer-salt complex formation.     

Pressure dependent Raman,and conductivity studies of the fast ion conductors Cu2HgI4, Ag2HgI4 and Tl2ZnI4

High pressure Raman, electrical conductivity, and optical microscopic studies on the ternary fast ion conductor Cu₂HgI₄ were undertaken to delineate the pressure-temperature phase diagram. In addition, comparison of the pressure dependence of Raman shifts in Cu₂HgI₄ and Tl₂ZnI₄ was used to assist in making vibrational assignments whenever possible.     

Evanescent waves in FGM spherical curved plates: an analytical treatment

A deep understanding of both guided propagating and evanescent waves is very essential for non-destructive evaluation. Guided propagating waves have received considerable attention, but the research on guided evanescent waves is quite limited, especially for functionally graded structures. This paper presents an analytical approach, based on the orthogonal function technique, to solve the evanescent waves in a spherical curved plate with functionally graded material in the radial direction. The proposed approach can obtain all the real, imaginary and complex solutions but without iterative process. The validity of the proposed approach is illustrated by comparison with available results. The convergence of the approach is also discussed through a numerical example. Dispersion characteristics of the guided waves in various graded spherical curved plates are studied and three dimensional dispersion curves are plotted in frequency-complex wavenumber space. The effects of different radius-thickness ratios and graded fields on the dispersion curves of the guided evanescent waves are illustrated. The displacement distributions are also discussed to analyze the characteristics of the guided evanescent waves.     

Perturbation of metal—metal stretching frequencies by the interaction of lewis acids with bridging carbonyls

Adduct formation on the oxygen of a bridging carbonyl causes a very small perturbation of metal—metal stretching frequencies of polynuclear carbonyls. This small shift contrasts with the large change in v(MM) when carbonyl groups are redistributed between terminal and bridging positions; therefore, using low frequency Raman spectroscopy, it is possible to infer the structural relation of C- and O-bonded adduct to the parent carbonyl. Structural inferences for Fe₃(CO)₁₂ · AlBr₃, Ru₃(CO)₁₂ · AlBr₃ and Fe₂(CO)₉ · AlBr₃ are given.     

Preparation and substitution chemistry of [Bu4N]2[W6Cl8(p-OSO2C6H4CH3)6]. A useful precursor for pseudohalide, acetate, and organometallic complexes containing the [W6Cl8](4+) core

The tosylate (p-toluenesulfonate) cluster [Bu4N]2[W6Cl8(p-OSO2C6H4CH3)6] (1) has been prepared and characterized by IR and NMR spectroscopy, elemental analysis, and an X-ray crystal structure. This cluster complex is shown to be a useful starting material for the preparation of pseudohalide clusters, [Bu4N]2[W6Cl8(NCQ)6] (Q = O (2), S (3), and Se (4)), in high yields. Cluster 1 also serves as a precursor to the new cluster compounds: [Bu4N]2[W6Cl8(O2CCH3)6] (5), [Bu4N]2[W6Cl8((mu-NC)Mn(CO)2(C5H5))6] (6), [W6Cl8((mu-NC)Ru(PPh3)2(C5H5))6][ p-OSO2C6H4CH3]4 (7), and [W6Cl8((mu-NC)Os(PPh3)2(C5H5))6][ p-OSO2C6H4CH3]4 (8). X-ray crystal structures are reported for 1, 4, and 5.     

Rhodium(I) catalyzed decomposition of formic acid

Rh(C₆H₄PPh₂)(PPh₃)₂ catalyzes the decomposition of formic acid to CO₂ and H₂. The initial step is the oxidative addition of formic acid to produce the intermediate Rh(HCO₂)(PPh₃)₃, which probably is followed by β-hydride elimination, to produce CO₂ and RhH(PPh₃)₃. The latter reacts with formic acid to produce H₂ and to reform Rh(HCO₂)(PPh₃)₃.     

Thermal and complex impedance analysis of amorphous and crystalline lithium salt mixtures

Amorphous electrolytes consisting of the lithium salts, Li[R-NSO₂CF₃] were prepared and the attendant low ionic conductivities of the lithium salt mixtures (1×10⁻⁶ S cm⁻¹ at room temperature) are attributed to high glass transition temperatures. An example is the novel amorphous salt, Li[18-C-6NSO₂CF₃] which produces an amorphous salt mixture with Li[N(SO₂CF₃)₂] (LiTFSI).