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1.
Characterization of the Protons in Polycrystalline Paratungstates using 1H MAS NMR Investigations 1H MAS NMR experiments are used to characterize the non‐acid protons of the anions in polycrystalline paratungstates by means of the measured isotropic chemical shift values. The investigation of various hydrates of ammonium paratungstate allows a direct proof of protons in NH4 ions and in water molecules while protons of the anions are not detectable. However, for both the potassium and the sodium paratungstates 1H MAS NMR investigations detected the protons of water molecules and the non‐acid protons of the paratungstate anions. Additional 1H broad‐line NMR experiments at 173 K support the interpretation of the results obtained by the 1H MAS NMR investigations. For the NMR signal of the non‐acid protons of the paratungstate anion in the 1H MAS NMR spectra of the potassium salt line‐splitting appears. This refers to the existence of two nonidentical positions of the protons in the crystal lattice and is in agreement with the results of the X‐ray structural analysis. 相似文献
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Roland Potz
Melanie Gldner Heiner Hückstdt Ursula Cornelissen Andreas Tutaß Heiner Homborg 《无机化学与普通化学杂志》2000,626(2):588-596
Synthesis and Structural Characterization of Boron Subphthalocyaninates Halosubphthalocyaninatoboron, [B(X)spc] (X = F, Cl, Br) is obtained by heating phthalonitrile with boron trihalide in quinoline (X = F) or the corresponding halobenzene, resp. [B(C6H5)spc] is prepared from phthalonitrile and tetraphenylborate or tetraphenyloboron oxide, resp. [B(OR)spc] (R = H, CH(CH3)2, C(CH3)3, C6H5) is synthesized by bromide substitution of [B(Br)spc] in pyridine/HOR. Substitution of [B(Br)spc] in carboxylic acids yields [B(OOCR)spc] (R = H, CX3 (X = H, Cl, F), CH2X (X = Cl, C6H5), C6H5). All subphthalocyaninates are characterized electrochemically and by UV‐VIS, IR/FIR, resonance Raman, and 1H/10B‐NMR spectroscopy. Typical B–X stretching vibrations are at 622 (X = Br), 950 (Cl), 1063 (F), 1096 cm–1 (OH) as well as between 1119 and 1052 cm–1 (OR) resp. 985 and 1028 cm–1 (OOCR). The difference ν(C=O)–ν(C–O) > 400 cm–1 confirms the unidentate coordination of the carboxylato ligands. According to the crystal structure analysis of [B(OH)spc], [B(OH)spc] · 2 H2O, [B(C6H5)spc], [B(OC(CH3)3)spc], [B(OOCCH3)spc] · 0.5 H2O · C2H5OH and [B(OOCCH3)spc] · 0.4 H2O · 1.1 C5H5N the spc ligand is concavely distorted. This saucer shaped conformation is independent of the acido ligands and the presence of solvate. The outermost C atomes are vertically displaced in part by more than 2 Å from the Ni plane. The B atom is in a distorted tetrahedral coordination geometry. It is displaced by ca 0.64 Å out of the Ni plane towards the acido ligand. The average B–N distance is 1.500 Å, and the B–O distances range from 1.418(5) to 1.473(2) Å. 相似文献
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tPreparation and Characterization of Lithiumhydrogenphthalocyanine Lithiumhydrogenphthalocyanine is obtained by the thermal decomposition of tetraalkylammoniumlithiumphthalocyanines as monoclinic blue needles (a = 19.081(9), b = 4,996(3), c = 14.437(7) Å; β = 119.64(4)° (from powder diffraction data)). The properties, IR and UV-VIS spectra are discussed. 相似文献
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Q. Xing W. Milius H. L. Krauss J. Blümel H. Hilbig F. H. Khler W. Strauß G. Bayreuther 《无机化学与普通化学杂志》1999,625(3):521-529
Surface Compounds of Transition Metals. XLI [1] Preparation and Properties of Organochromium Compounds by Reaction of Phillips Catalysts with Ethylene Reaction of reduced Phillips catalysts with ethylene at 300 °C deactivates the catalyst; supported organochromium compounds are formed. These can be cleaved from the silica support by HCl and other acids, and transferred into solution by extraction with CH3OH. Chromatography yields fractions of organochromium compounds which differ by CH2 moieties. XPS, 1/2H NMR, and mass spectra as well as magnetic measurements prove that an ensemble of (RnCp)CrCl2(CH3OH) (RnCp = alkylated cyclopentadienyl) has been formed. The RnCp ligand results from a chromium‐assisted oxidative coupling of the olefin with or without CC‐cleavage. According to UV/Vis and mass spectroscopy Cl– and CH3OH can be substituted for other anions and donor molecules. Without a donor dinuclear, Cl‐bridged molecules are obtained, of which [(1,2,3‐Me3Cp)CrCl2]2 was established by crystal structure analysis. Reaction with O2 reversibly leads to chromium(V) compounds of the type (R2Cp)Cr(O)Cl2. 相似文献
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Preparation and Spectroscopic Characterization of Carboxylatododecaborates The tetrabutylammonium salt (TBA)2[B12H12]2? reacts with formic, acetic, cyanoacetic, phenylacetic, propionic, butyric, and thioacetic acid at temperatures between 80 and 150°C forming the carboxylatododecaborates [(RC(O)O)n? B12H12? n]2?, n = 1, 2, [CH3C(O)S? B12H11]2?. The isolation of the pure compounds is achieved by ion exchange chromatography on diethylaminoethyl cellulose. In case of the dicarboxylatododecaborates beside the 1,7-isomer predominantly the 1,2-isomer, while 1,2-[(OH)C6H5CH2C(O)O? B12H10]2? is formed exclusively. The alcaline hydrolysis of [RC(O)O? B12H11]2? and 1,2-[(OH)C6H5CH2C(O)O? B12H10]2? results in [(OH)? B12H11]2? and 1,2-[(OH)2? B12H10]2?. All compounds are characterized by their 11B-nmr, 13C-nmr and IR spectra. The 11B-nmr signals are assigned by a sheme allowing to establish expected spectra. 相似文献
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Preparation and Characterization of Calcium Hydrogen Sulfate CaSO4 · H2SO4 was identified as calcium hydrogen sulfate whereas CaSO4 · 3 H2SO4 is an adduct of CaSO4 with H2SO4. Depending on the excessive amount of H2SO4 both compounds exist side by side up to a temperature of 343 K, whereas above this temperature only Ca(HSO4)2 is stable. The DTA curve of Ca(HSO4)2 shows two maxima at 488 K and 523 K, according to the separation of H2O under formation of pyrosulfate and decomposition of this compound under elimination of SO3. In comparison with other hydrogen sulfates Ca(HSO4)2 shows a considerable increased O? H distances. The d-values of Ca(HSO4)2 are calculated and represented. 相似文献
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Synthesis, Properties, and Molecular Structures of Alkylaluminium Aminoalkoxide Chlorides Alkylaluminium aminoalkoxide chlorides [R(Cl)AlOR*] 1 – 3 have been obtained from the reaction of dialkyl aluminium chlorides R2AlCl with the respective aminoalkohol HOR* ( 1 : R = Et, OR* = dimethylamino‐1‐propanol; 2 : R = Me, OR* = (+);(–)‐dimethylamino‐2‐propanol; 3 : R = Me, OR* = (S)‐N‐methyl‐2‐pyrrolidinyl‐methanol). The reaction between dimethylaluminium chloride and (S)‐α, α‐diphenyl‐2‐pyrrolidinyl‐methanol (OR* = Dpm) yielded, by contrast, the ionic {[MeAl(OR*)2AlMe2]+ [MeAlCl3]–} complex ( 4 ). 1 – 4 have been characterised by 1H, 13C and 27Al‐NMR spectroscopy. Crystal structures of 1 and of the 1 : 1 solvate of 4 with Et2O have been determined by X‐ray methods and the absolute structure of 4 was confirmed by refinement of the Flack‐parameter. The dimeric molecules of 1 are composed of two chelating rings linked via an almost planar Al2O2 unit and pentacoordination is observed about aluminium. In contrast, each of the two crystallographically independent cation molecules of 4 contains one four‐ and and one five‐coordinate metal centre. 相似文献
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Darstellung und Charakterisierung einige Thiocyanat- und Selenocyanat-Komplexe von Übergangsmetallen
Some 6:1 thiocyanate complexes of FeIII, MoIII, RuIII, OsIII, IrIII and some 6:1 or 4:1 selenocyanate complexes of FeII, FeIII, MoIII, RhIII, PdII, PtII, and AuIII have been prepared as salts of large organic cations. The compounds are characterized by their infra-red spectra and by conductance measurements. In particular the linkage property of the thiocyanate and selenocyanate ligand is discussed together with the consequences it has on the AHRLAND -CHATT -DAVIES -PEARSON classification of the central ions. 相似文献
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Synthesis and Characterization of Tetralithiumpentaoxoselenate(VI) Pure Li4SeO5 was prepared by solid state reaction at 500 °C from a mixture of Li2O and Li2SeO4 in silver crucibles. The crystal structure was solved and refined with x‐ray powder methods (profile matching, C2/c, a = 873.3(1), b = 572.5(1), c = 783.6(1) pm, β = 98.29(1)°, Rp = 0.052, Rwp = 0.066). Li4SeO5 contains novel SeO54– anions, which form slightly distorted trigonal bipyramids. All ions are coordinated by 5 ligands in the shape of trigonal bipyramidal polyhedra, according to the formula Li4[5]Se[5]O5[5]. From the empirical formula and the coordinaton environments, it is clear that this is an order variant of the A[5]B[5] structure type, that was found in the system NaCl by global optimisation methods. The crystal structure is consistent with spectroscopic data (IR, Raman, NMR). The ionic conductivity (σ = 3.34 10–5 Ω–1 cm–1 at 340 °C) of the compound was determined with impedance measurements. 相似文献
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Synthesis, Crystal Structure, Vibrational Spectra, and Normal Coordinate Analysis of (Ph4P)2[OsN(N3)5] and 15N NMR Chemical Shifts of Nitridoosmates(VI, VIII) The treatment of (Ph4P)[OsNCl4] with NaN3 yields (Ph4P)2[OsN(N3)5], which crystal structure has been determined by single crystal X‐ray diffraction analysis (monoclinic, space group P 21/a, a = 20.484(6), b = 11.168(1), c = 20.666(4) Å, β = 97.35(3)°, Z = 4). The IR and Raman vibrations were assigned by a normal coordinate analysis based on the molecular parameters of the X‐ray determination. The valence force constants are fd(Os≡N) = 8.52, fd(Os–Nα) = 1.99, fd(Nα–Nβ) = 12.42, fd(Nβ–Nγ) = 12.73 and for the azido ligand in trans‐position to the nitrido group fd(Os–Nα · ) = 1.84, fd(Nα · –Nβ · ) = 11.91, fd(Nβ · –Nγ · ) = 12.18 mdyn/Å. The 15N NMR spectra of various nitridoosmates reveal the chemical shifts δ(15N) for K[OsO315N] = 387.6, K2[Os15NCl5] = 446.7, (Ph4P)[Os15NCl4] = 352.9, [(n‐C6H13)4N]2[Os15N(N3)5] = 307.3 and for [(n‐Pr)4N]2[Os15N(15NCO)5] = 483,7 (Os≡N), –417,7 (OsNCOeq) und –392,8 ppm (OsNCOax). 相似文献
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Syntheses and Reactions of Aluminium Alkoxide Compounds Al(OcHex)3 ( 1 ) can be synthesized by the reaction of Al with cyclohexanol under evolving of H2 in boiling xylene. [Li{Al(OCH2Ph)4}] ( 2 ) was obtained by treatment of PhCH2OH with a 1 M solution of LiAlH4 in THF. [{(THF)Li}2{Al(OtBu)4}Cl] ( 3 ) is the result of the reaction of four equivalents of LiOtBu on AlCl3 in THF. 3 is the educt for the reactions with the Lewis‐acids InCl3 and FeCl3 in THF leading to the metalates [{(THF)2Li}2{Al(OtBu)4}] · [MCl4] [M = In ( 4 ), Fe ( 5 )]. The attempt to react InCl3 with four equivalents of LiOtBu leads to only one isolated and characterized product, the complex [Li4(OtBu)3(THF)3Cl]2 · THF ( 6 · THF), which can also be synthesized by the treatment of LiCl with three equivalents of LiOtBu in THF. 1–6 · THF were characterized by NMR, IR and MS techniques as well as by X‐ray structure determinations. According to them, 1 , which is tetrameric in solution, is the first structurally characterized example of the proposed trimer form of aluminium alkoxides [ROAl{Al(OR)4}2] with a central trigonal bipyramidal coordinated Al atom. 2 forms a coordination polymer with a distorted tetrahedral coordination sphere of Li and Al, running along [100]. The trinuclear structure skeleton [{(THF)2Li}2{Al(OtBu)4}]+ is still present in the isotypical metalates 4 and 5 . The counter ions [MCl4]– possess nearly Td symmetry. The remarkable structural motif of 6 · THF are two heterocubanes [Li4(OtBu)3(THF)3Cl] dimerized by Li–Cl bonds. 相似文献
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Preparation, isolation, and characterization of Monoseleane and Disulphane-Diphosphonate The barium salts of monoselenane and monotellurane disulphanediphosphonate are isolated in pure state for the first time. They are characterized by analytical data and i.r. spectra. 相似文献
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Susanne Knoll Rolf Borsdorf Frank Tschwatschal Thomas Gelbrich Thomas Ristau 《无机化学与普通化学杂志》1997,623(12):1959-1967
Synthesis and Characterization of Configurationally Stable Diorganotin(IV) Complexes with Tin as a Chiral Centre Contrary to the high optical stability of tetraorganotin compounds most heteroleptic organic tin compounds are configurationally instable. We report the synthesis and the characterization of some new enantiomeric and diastereomeric diorganotin(IV) complexes of stable configuration with tin as a chiral centre. The stabilization of the chiral tin atom was realized by complexation with tridentate diacidic esterhydrazone ligands H2L, which prevent an interconversion at the stereogenic centre. Multinuclear NMR-studies in solution demonstrate, that the configuration of the chiral tin center is configurationally stable up to 160°C. The molecular structure of the complexes Neophyl-phenyl-tin-2[(2-methyl-mercaptothiocarbonyl)-hydrazono]propionate II b and (2-Methyl-butyl-1-yl)-phenyl-tin-[S-methyl-β-N-(2-salicylmethylidene)thiocarbazat] III g have been determined by single crystal X-ray diffraction analysis. 相似文献
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Synthesis and Characterization of Sodium Cyanamide The synthesis of Na2CN2 was carried out by reaction of sodium amide with sodium hydrogen cyanamide at 200 °C, in vacuum. Single crystals were obtained while heating the product (500 °C, 8 days) in silver crucibles. The title compound was characterised by single crystal X‐ray diffraction and IR‐spectroscopy (C2/m; Z = 2, a = 5.0456(3), b = 5.0010(3), c = 5.5359(3) Å; β = 110.078(5)°; R1 = 3.18%, wR2 = 6.35%, GOF = 1.078). The CN22– units are linear exhibiting a C–N bond length of 1.236(1) Å, while sodium is coordinated by five nitrogen atoms forming a square pyramid. The structural relationships to aristotypic Na2HgO2 are pointed out. 相似文献
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Preparation, Isolation, and Characterization of Ba@C74 For the first time Ba@C74 has been isolated in pure form. The title compound has been isolated from a raw material, produced in a radio‐frequency‐furnace, consisting of a mixture of fullerenes and endohedral Bariumfullerenes. Ba@C74 was separated by two stage sublimation and subsequent high‐performance liquid chromatography (HPLC) using a Buckyprep column. The capacity factor for Ba@C74 is 6.0. Its endohedral character has been deduced from the fragmentation pattern obtained by time‐of‐flight mass spectroscopy while the composition has been confirmed by comparison of calculated and measured isotopic pattern of the parent peak. Further characterization was performed by VIS/NIR‐spectroscopy and electron‐paramagnetic‐resonance spectroscopy (EPR). 相似文献
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Preparation and Spectroscopic Characterization of Fluorotrichloroarsonium Hexafluoroarsenate, AsFCl3+AsF6? The mixed halide pniktide cation AsFCl3+ is prepared by oxidative fluorination of AsCl3 with XeF+ AsF6?. AsFCl3+ AsF6? is characterized by IR, Raman, and 19F-NMR spectroscopy. 相似文献
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1,1′‐Bis(trimethylsilylamino)ferrocene reacts with trimethyl‐ and triethylgallium to give the μ‐[ferrocene‐1,1′‐diyl‐bis(trimethylsilylamido)]tetraalkyldigallanes. These were converted into the 1,3‐bis(trimethylsilyl)‐2‐alkyl‐2‐pyridine‐1,3,2‐diazagalla‐[3]ferrocenophanes, of which the ethyl derivative was characterized by X‐ray structural analysis. Treatment of gallium trichloride with N,N′‐dilithio‐1,1′‐bis(trimethylsilylamino)ferrocene affords μ‐[ferrocene‐1,1′‐diyl‐bis(trimethylsilylamido)]tetrachlorodigallane along with bis(trimethylsilyl)‐2,2‐dichloro‐1‐aza‐3‐azonia‐2‐gallata‐[3]ferrocenophane as a side product, and both were structurally characterized by X‐ray analysis. The solution‐state structures of the new gallium compounds and aspects of their molecular dynamics in solution were studied by NMR spectroscopy (1H, 13C, 29Si NMR). 相似文献