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61.
The conformational properties of diastereomeric P-modified nucleotides are reported as reflected by different NMR parameters. Some conformational trends can be rationalized by consideration of the 3J(C4,P) and 3J(C2,P) coupling values of the isomers and the nature of the substituent on the phosphorus. Configurational assessment of the phosphorus is inferred from NOE experiments. The effects of temperature, solvent and size of substituents are presented. 相似文献
62.
F. Preuss M. Steidel M. Vogel G. Overhoff G. Hornung W. Towae W. Frank G. Reiß S. Müller-Becker 《无机化学与普通化学杂志》1997,623(8):1220-1228
Phosphane, Phosphite, Phosphido, Complexes of Vanadium(V) Complex formation of tert-butylimidovanadium(V)trichloride ( 1 ) with phosphanes und phosphites has been studied. Syntheses of phosphidovanadium(V) compounds tC4H9N?VCp(NHtC4H9)[P(SiMe3)2] and tC4H9N?VCp(NiProp2)(PR2) (R?SiMe3, Ph) are described starting from the corresponding chlorovanadium(V) complexes. The reaction of 1 with silver hexafluorophosphate yields a bis(fluoro)phosphidovanadium(IV complex [(μ-PF2)2V2Cl2)(NtC4H9)2]; as primary intermediate product of the unknown redox reaction a cationic vanadium(V) complex [tC4H9N?VCl2 · PPh3]+PF6? has been isolated. 1 reacts with an excess of diisopropylamine forming tC4H9N?V(NiProp2)Cl2 ( 16 ); in addition the following diisopropylamido-tert-butylimidovanadium(V) compounds tC4H9N?VCp(NiProp2)Cl ( 3 ) and tC4H9N?V(NiProp2)X2 (X?CH2CMe3, OtC4H9, CH3COO) has been prepared. All compounds obtained are characterized by 1H, 51V, 31P NMR spectroscopy. The X-ray diffraction analysis of 16 and 3 indicate a planar coordination sphere of the amido nitrogen atom. 相似文献
63.
A New Tricyclic Sulfur-rich Phosphane From the products of the reaction of P4S3 with tert-Butyliodide the compound (t-Bu(S)P)2P4S3 was isolated in low yield. The compound is stable and has a structure related to the hydrocarbon brexane. By reaction with triphenylphosphin the compounds (t-BuP)(t-Bu(S)P)P4S3 and (t-BuP)2P4S3 were obtained. The 31P-nmr spectra of all compounds were solved and used to determine the structure of the molecules. A complete set of 31P-nmr data is given. 相似文献
64.
In 1977 the celebrated theorem of B. Dahlberg established that the harmonic measure is absolutely continuous with respect to the Hausdorff measure on a Lipschitz graph of dimension in , and later this result has been extended to more general non-tangentially accessible domains and beyond.In the present paper we prove the first analogue of Dahlberg's theorem in higher co-dimension, on a Lipschitz graph Γ of dimension d in , , with a small Lipschitz constant. We construct a linear degenerate elliptic operator L such that the corresponding harmonic measure is absolutely continuous with respect to the Hausdorff measure on Γ. More generally, we provide sufficient conditions on the matrix of coefficients of L which guarantee the mutual absolute continuity of and the Hausdorff measure. 相似文献
65.
《Magnetic resonance in chemistry : MRC》2018,56(4):276-284
Multinuclear solid‐state NMR and powder X‐ray diffraction data collected for phosphonate materials Zr(O3PC6H4PO3) · 3.6H2O and Sn(O3PC6H4PO3)0.85(O3POH)0.30 · 3.09H2O have resulted in the layered structure, where the phosphonic acids cross‐link the layers. The main structural motif (the 111 connectivity in the PO3 group) has been established by determination of chemical shift anisotropy parameters for phosphorus nuclei in the phosphonate groups. An analysis of the variable‐temperature 31P T1 measurements and the shapes of the phosphorus resonances in the 31P static NMR spectra have resulted in the dipolar mechanism of the phosphorus spin‐lattice relaxation, where the rotating phenylene rings reorient dipolar vectors P…H as a driving force of the relaxation process. It has been found that water protons do not affect the 31P T1 times. The activation energy of the phenylene rotation in both compounds has been determined as low as 12.5 kJ/mol. The interpretation of the phosphorus relaxation data has been independently confirmed by the measurements of 1H T1 times for protons of the phenylene rings. 相似文献
66.
Tahya Bamine Edouard Boivin Christian Masquelier Laurence Croguennec Elodie Salager Dany Carlier 《Magnetic resonance in chemistry : MRC》2020,58(11):1109-1117
7Li, 31P, and 19F solid-state nuclear magnetic resonance (NMR) spectroscopy was used to investigate the local arrangement of oxygen and fluorine in LiVPO4F1-yOy materials, interesting as positive electrode materials for Li-ion batteries. From the evolution of the 1D spectra versus y, 2D 7Li radiofrequency-driven recoupling (RFDR) experiments combined, and a tentative signal assignment based on density functional theory (DFT) calculations, it appears that F and O are not randomly dispersed on the bridging X position between two X–VO4–X octahedra (X = O or F) but tend to segregate at a local scale. Using DFT calculations, we analyzed the impact of the different local environments on the local electronic structure. Depending on the nature of the VO4X2 environments, vanadium ions are either in the +III or in the +IV oxidation state and can exhibit different distributions of their unpaired electron(s) on the d orbitals. Based on those different local electronic structures and on the computed Fermi contact shifts, we discuss the impact on the spin transfer mechanism on adjacent nuclei and propose tentative signal assignments. The O/F clustering tendency is discussed in relation with the formation of short VIVO vanadyl bonds with a very specific electronic structure and possible cooperative effect along the chain. 相似文献
67.
《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):2309-2317
Complexes of beryllium chloride and nitrate with (Me2N)2P(O)F were characterized in solution by multinuclear NMR spectroscopy and in some cases by IR spectroscopy and conductimetry. 31P and 19F NMR spectra were informative of changes associated with complex formation revealing resonances consistent with different species in solution and suggest an equilibrium between these species in both beryllium derivatives. These compounds show narrow lines in the solution 9Be NMR spectra, indicative of a highly symmetric environment for beryllium. The presence of the different species was more pronounced in beryllium chloride complexes. The results are compared to those reported in the literature for hexamethylphosphoramide (HMPA). 相似文献
68.
《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):2349-2356
Seven new 1-fluorinated-4-phosphopyrazoles 2 have been prepared in 60–94% yield by cyclization of N-(2′,2′,2′-trifluoroethyl) phosphonyl β-hydrazones 1 with triethyl orthoformate in the presence of acetic acid. The IR data, the 1H, 13C, 19F, 31P chemical shifts and coupling constants of the compounds 2 are reported. 相似文献
69.
Günter Paulus Schiemenz 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):185-202
Abstract Contrary to claims in the literature, the 31P NMR signal positions of ortho-dimethylaminomethyl-substituted triarylphosphines do not provide evidence for hypercoordination at phosphorus; the observed highfield shifts relative to triphenylphosphine are rather due to the ortho-effect. In (8-dimethylamino-naphth-1-yl)phosphines, the signal positions similar to that of triphenylphosphine are the result of the highfield ortho-effect and a lowfield peri-substituent effect of about the same magnitude whose nature remains to be explored. 相似文献
70.
Fatma S.M. Hassan 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2):406-417
Complexes of the type [Pt R2 (dppma-PP′)] (R─Me, Et, Ph, CH2Ph, C6H4 Me-p, C6H4OMe-2, CH2CMe3, 1-naphthyl, C6H4Me-o, dppma = Ph2PNMe PPh2) have been prepared from [PtCl2, (dppma-PP′)] and the corresponding alkyl-lithium or Grignard reagents. Equilibrium constants, k, for the conversion of [PtR2 (dppma-PP′)] into cis-[PtR2(dppma-P)2] with dppma were studied using 31P NMR spectroscopy at room temperature. Equilibrium is rapidly established for R─C6H4-Me-o, at 20°C. Complex of the type cis-[PtR2 (dppma-P)2] was isolated R─C6H4 Me-o. The complexes [PtMe2(dppma-P)2] and [Pt(o-methoxyphenyl)2(dppma-P)2] were prepared, but unfortunately decomposed once isolated, the only evidence for its formation being from 31P-{1H} NMZR spectroscopy. The o-tolyl or 1-naphthyl complexes exist as syn-anti mixtures in solution, due to restricted rotation around the platinum aryl bonds. Treatment of several complexes of the type [PtR2(dppma-PP′)] with MeI gives [PtR2Me(I)(dppma-PP′)] with trans addition of MeI. Treatment of [PtR2(dppma-PP′)] with HCl gives [Pt Cl (R) (dppma-PP′)] for R─C6H2Me3-2,4,6, C6H4-CH3-2, C6H4-Me-4, Me, 1-naphthyl. The 1H, 31P NMR parameters for these complexes are discussed. Attempted preparation of complexes of the type [PtR2 (dppma-P)2M] (R─C6H4-Me-2, Me CN-C6H4-Me-4); M─Pd, Pt, Au,) are reported. 相似文献