Search results for "Spectroscopy"
showing 10 items of 10293 documents
Selective Crystallization of Dimeric vs. Monomeric Dimethyltin‐Containing Tungstoarsenates(III) and ‐antimonates(III) with the Guanidinium Cation
2009
The use of guanidinium cations [C(NH 2 ) 3 ] + as crystallizing agents allowed us to selectively isolate the dimeric [{(CH 3 ) 2 -Sn(H20)} 4 {(CH 3 ) 2 Sn}(B-β-XW 9 O 33 ) 2 ] 8- (1, X = As III ; 2, X = Sb III ) polyanions from the reaction of (CH 3 ) 2 SnCl 2 with Na 9 [B-a-XW 9 O 33 ) (3:1 ratio) in water at pH 3. This reaction is known to give the monomeric [{(CH 3 ) 2 Sn(H 2 O) 2 } 3 (B-β-XW 9 O 33 )] 3- polyanions as the major species. Polyanions 1 and 2 are composed of one octahedral trans-(CH 3 ) 2 SnO 4 moiety that bridges two trilacunary [B-β-XW 9 O 33 ] 9- Keggin subunits further decorated by two structurally nonequivalent {(CH 3 ) 2 Sn} 2+ functionalities each: one distorted octa…
Molecular materials with conducting and magnetic properties based on ET and [ M(tdas)2]x-dithiolenes
2004
Two hybrid molecular materials showing a combination of magnetic and conducting properties, the charge-transfer (ET) 2 [Fe(tdas) 2 ] (1) and (ET)Ni(tdas) 2 (2), (ET=bis(ethylenedithio) tetrathiafulvalene; M=Fe, Ni; tdas=l,2,5-thiadiazole-3,4-dithiolate) salts, are characterized by vibrational (IR and Raman) and UV-VIS-NIR spectroscopies. These studies have proved to be effective and diagnostic tools in identifying the oxidation state (partial or integer) and the packing pattern (dimers or segregated stacks) of the ET donor only, since no v(C=C) group vibration sensitive to the charge of M(tdas) 2 complexes has been observed. This is ascribed to the extensive electron-delocalization inside t…
Nucleophilic attack within Ge, Sn and Pb complexes containing Me2N(CH2)(3) - as a potential intramolecular donor ligand
1998
Abstract Thirteen tin compounds LxPhySnClz and LPh2SnPhX (x=1–4, y=0–3, z=0–2, XPh, F, Cl, Br, I, OPh), six germanium compounds LxPhyGeClz and four lead compounds LPh2PbPhX (XPh, Cl, Br, I) containing the potential intramolecular donor LMe2N(CH2)3—have been synthesized by Grignard reactions, redistribution, halogenation, exchange of halide and phenylation. Evidence for 1,5-chelation in which the donor Me2N intramolecularly attacks the Lewis-acidic atoms Ge, Sn or Pb is provided by six crystal structure determinations: Me2N(CH2)3SnPh2Cl, 5; Me2N(CH2)3SnPh2Br, 5a; Me2N(CH2)3SnPh2I, 5b; Me2N(CH2)3SnPh2OPh, 5d; Me2N(CH2)3SnPh3·HCl·H2O. 1a; Me2N(CH2)3PbPh2I, 17b), and by solution 13C, 119Sn a…
Über antimon-haltige heterocyclen
1980
Abstract p -Nitrophenyl- and p -tolyl-oxadithia- and trithiastibocanes have been synthesized from the respective aryldichlorostibane and dithiole. The compounds have been characterised by means of 13 C NMR and vibrational spectra (ν(SBS 2 ) 350–320 cm −1 ). The crystal structure of p -nitrophenyltrithiastibocane has been determined ( R = 0.042). The eight-membered ring exhibits a boat-chair conformation. Single-bond distances of SbC and SbS (219, 244 and 245 pm), a 1,5-transannular Sb⋯S interaction (319 pm), and Sb⋯S and Sb⋯O (339 and 353 pm) intermolecular contacts, result in a six-coordinated Sb III (ψ-monocapped octahedral) species. The two additional Sb⋯S distances are in accordance w…
Über polygermane
1986
Abstract The optimum conditions for the synthesis of the trigermanes Ge3Ph8 and Ge3Me2Ph6 according to R2GeCl2 + 2 Ph3GeAk (Ak = Li, K) in HMPT have been determined. The main difficulty is to repress a nucleophilic attack of Ph3Ge− at newly formed GeGe bonds. The mass spectrum of Ge3Me2Ph6 shows rearrangements of the GePh3 and Ph/Me groups. The 13C NMR phenyl signals of di-, tri- and tetra-germanes are nearly identical. Ge3Ph8 and Ge4Ph10 transform to the plastically-crystalline state before melting (ΔH 45.3 and 54.9 kJ mol−1). The crystal structure of Ge3Me2Ph6 has been determined. The molecule has C2 symmetry (GeGe 242.9(1) pm, GeGeGe 120.3(1)°).
Assignment of the Absolute Configuration and Total Synthesis of (+)-Caripyrin
2014
The antifungal secondary metabolite (+)-caripyrin was studied by vibrational circular dichroism spectroscopy. Analysis of the recorded data, with the Boltzmann weighted-average of the spectra calculated at the B3LYP/6-311G(d,p) level of theory for all relevant conformers, unequivocally proved the (R,R)-configuration for the dextrorotatory natural product. Based on this finding, a short enantioselective synthesis of (+)-caripyrin was developed.
Relaxational dynamics at the class transition in orientational and canonical glasses investigated by dielectric spectroscopy
1991
Abstract Measurements of the dielectric permittivity are reported for the canonical glass glycerol and for solid solutions of ferroelectric betaine phosphite and ferroelectric betaine phosphate, which can be viewed as protype systems of orientational glasses. In this latter system long range dipolar order is suppressed by the competing ferroelectric and antiferroelectric interactions and the dipolar moments freeze-in devoid of long range order. In both systems the relaxation dynamics is studied for frequencies 10−2Hz≤ν≤106Hz, close to the glass transition temperature. The relaxation dynamics is characterized according to Angell's classification scheme of strong and fragile glass-formers.
Oxo-Vanadium(IV) Dihydrogen Phosphate: Preparation, Magnetic Study, and Heterogeneous Catalytic Epoxidation
2008
A layered oxo-vanadium(IV) dihydrogen phosphate, {VO(H2PO 4)2} n has been synthesized hydrothermally and characterized by several physicochemical methods. Single-crystal X-ray analysis (crystal system, tetragonal; space group, P4/ ncc; unit cell dimensions, a = b = 8.9632(4), c = 7.9768(32) A) of {VO(H2PO4) 2} n reveals that the compound has an extended two-dimensional structure. The VO2+ moieties are connected through bridging H 2PO4 (-) ions, and this type of connection propagates parallel to the crystallographic ab plane which gives rise to a layered structure. The layers are staked parallel to the crystallographic c axis with a separation between the layers of ca. 4.0 A. Magnetic suscep…
Complexes of organometallic compounds
1974
Abstract Several new complexes formed by PhTlCl 2 with tridentate ligands (with ONO and SNO donor atoms) and a tetradentate ligand (with ONNO donor atoms), have been prepared. The complexes show 1/1 organothallium(lll)/Ligand ( = L 2− ) stoichiometry. Their nature and configuration are investigated in the solid state by vibrational spectroscopy, and in solution by electronic spectroscopy. The existence of chelation by the dianionic ligands on Tl III is inferred, and suggestions are made concerning the Tl III coordination number and the stereochemistry of the complexes.
Selenium Imides: 77Se NMR Investigations of the SeCl2−tBuNH2 Reaction and X-ray Structures of Se3(NtBu)3, tBuNSe(μ-NtBu)2SO2, and tBuNSe(μ-NtBu)2SeO
2000
The reaction of SeCl2 with tert-butylamine in various molar ratios in THF at −78 °C has been investigated by 77Se NMR spectroscopy. In addition to the known Se−N heterocycles Se6(NtBu)2 (1) and Se9(NtBu)6 (2), the acyclic imidoselenium(II) dichlorides ClSe[N(tBu)Se]nCl (4, n = 1; 5, n = 2) and two new cyclic selenium imides [Se3(NtBu)2]n (3, n = 1 or 2) and Se3(NtBu)3 (6) have been isolated and identified. An X-ray analysis shows that 6 is a six-membered ring in a chair conformation with |d(Se−N)| = 1.833 A. Crystal data: 6, trigonal, P3c1, a = 9.8660(3) A, c = 20.8427(7) A, V = 1757.0(1) A3, Z = 6. The 1H, 13C, and 77Se NMR data for 1−6 are reported, and some reassignments of earlier lite…