A 19F nuclear magnetic resonance study of the conjugate Brönsted-Lewis superacid HSO3F-SbF5. Part 1

1999 ◽  
Vol 77 (11) ◽  
pp. 1869-1886 ◽  
Author(s):  
Dingliang Zhang ◽  
Markus Heubes ◽  
Gerhard Hägele ◽  
Friedhelm Aubke
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Nmr Spectra ◽  
Nuclear Magnetic Resonance Study ◽  
Magnetic Resonance Study ◽  
Formation Reaction ◽  
H Nmr ◽  
Acid Conjugate ◽  
Nmr Methods ◽  
Cis And Trans

The Brönsted-Lewis superacid HSO3F-SbF5 or "magic acid" is re-investigated by modern 19F NMR methods over a wide concentration range. The system is found to be considerably more complex than had been assumed previously. A total of 13 different anions are identified of which only five have previously been identified in magic acid. With increasing SbF5 contents the concentration of monomeric anions like [SbF6]-, [SbF5(SO3F)]-, cis- and trans-[SbF4(SO3F)2]-, and mer-[SbF3(SO3F)3]- gradually decreases. Except for [Sb2F11]-, which is present in very small concentrations only, the formation of oligomers involves exclusively μ-fluorosulfato bridges. In addition to donor (SO3F)- and acceptor (SbF5) complex formation to give [SbF5(SO3F)]- and possibly ligand redistribution, the solvolysis of SbF5 or SbF4(SO3F) in HSO3F appears to be the principal formation reaction for polyfluorosulfatofluoroantimonate(V) anions. In glass (NMR tubes) the solvolysis product HF is converted to the oxonium ion [H3O]+, which has previously been identified by 1H NMR and structurally characterized as [H3O][Sb2F11] by us.Key words: magic acid, conjugate superacid, fluorosulfuric acid, 19F NMR spectra.

A nuclear magnetic resonance study of Al–Mn quasicrystals and related materials

1987 ◽  
Vol 2 (4) ◽  
pp. 431-435 ◽  
Author(s):  
Keith R. Carduner ◽  
B. H. Suits ◽  
J. A. DiVerdi ◽  
Michael D. Murphy ◽  
David White
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Melt Spinning ◽  
Nmr Spectra ◽  
Nuclear Magnetic Resonance Study ◽  
Magnetic Resonance Study ◽  
Broad Distribution ◽  
Quadrupole Field ◽  
Melt Spinning Technique ◽  
Nuclear Magnetic

Nuclear magnetic resonance (NMR) results are presented for several aluminum alloy samples prepared using the melt-spinning technique including orthorhombic Al6Mn, Al–Mn quasicrystals both with and without doping with Si and Ru, and a T-phase alloy of Al and Pt. With the exception of the orthorhombic material, all of the NMR spectra show a broad distribution of sites. No features unique to the quasicrystal phase are observed. For the orthorhombic material the quadrupole field parameters are found to be ∥VQ∥ − 1.0±0.1 MHz and η = 0.4±0.1.

α-N,N-Dimethylaminoethylferrocene. A nuclear magnetic resonance study relating to stereoselective metalation

1986 ◽  
Vol 64 (4) ◽  
pp. 667-669 ◽  
Author(s):  
Ian R. Butler ◽  
William R. Cullen ◽  
F. Geoffrey Herring ◽  
N. R. Jagannathan
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Spatial Correlation ◽  
Nuclear Magnetic Resonance Study ◽  
Magnetic Resonance Study ◽  
H Nmr ◽  
Nmr Study ◽  
Nuclear Magnetic

A 1H nmr study of Fe(C5H4CHMeNMe2-η)(C5H4PPh2-η), 2, using the nOe difference experiment, shows a spatial correlation between the —NMe2 group and the site of stereoselective lithiation.

An optical stopped-flow and 1H and 113Cd nuclear magnetic resonance study of the kinetics and stoichiometry of the interaction of the lanthanide Yb3+ with carp parvalbumin

1983 ◽  
Vol 61 (8) ◽  
pp. 860-867 ◽  
Author(s):  
David C. Corson ◽  
Lana Lee ◽  
Gerard A. McQuaid ◽  
Brian D. Sykes
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Rate Constants ◽  
Calcium Binding ◽  
Relative Displacement ◽  
Nuclear Magnetic Resonance Study ◽  
Stopped Flow ◽  
H Nmr ◽  
Nmr Methods ◽  
Nuclear Magnetic

The rate constants for the dissociation of the lanthanide Yb3+ from the CD and EF calcium-binding sites of carp parvalbumin (isoelectric point, 4.25) have been measured using optical stopped-flow and 1H nuclear magnetic resonance (NMR) methods. The off-rate constants for Yb3+ are 1.5 × 10−1 and 1.3 × 10−3 s−1 respectively, at pH 6.6 and 23 °C. The relative displacement of Ca2+ from the two sites by Yb3+ was determined from the observed amplitude of the fast and slow kinetic phases. Yb3+-shifted 1H-NMR spectra of parvalbumin are presented as a function of pH, concentration, and H2O:D2O ratio to relate the NMR results to the kinetic and optical results. The displacement of Cd2+ from parvalbumin by Yb3+ was studied using 113Cd NMR. All of the results show the sequential displacement of Ca2+ from the CD and EF sites of parvalbumin by Yb3+. Some results are also presented for Tb3+ and Gd3+.

Synthesis and nuclear magnetic resonance study of the compounds (2-X-1,3-dithiane) (X = H, Me, SiMe3, GeMe3, SnMe3, PbMe3) and their tetracarbonyliron complexes

1978 ◽  
Vol 56 (11) ◽  
pp. 1538-1544 ◽  
Author(s):  
David J. Cane ◽  
William A. G. Graham ◽  
Liviu Vancea
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Nmr Spectroscopy ◽  
Magnetic Resonance ◽  
Energy Barrier ◽  
Nmr Spectra ◽  
Nuclear Magnetic Resonance Study ◽  
Carbonyl Groups ◽  
Magnetic Resonance Study ◽  
Ring Inversion ◽  
C Nmr

A series of (1,3-dithiane)Fe(CO)4 complexes, (2-X-1,3-dithiane)Fe(CO)4, X = H, Me, SiMe3, GeMe3, SnMe3, PbMe3, has been prepared and characterized, and both the complexes and the free ligands studied by 1H and 13C nmr spectroscopy. The energy barrier to ring inversion in (1,3-dithiane)Fe(CO)4, ΔG298†, is 14.7 ± 0.2 kcal mol−1, some 4.4 kcal mol−1 higher than in free 1,3-dithiane.13C nmr spectra showed that within the Fe(CO)4 moiety, rapid averaging of carbonyl groups occurs down to at least −80 °C.

Halogen and pseudohalogen substitution of some adamantanoid chalcogenate clusters [(μ-EPh)6(MEPh)4]2− using methylmercury and triphenyltin derivatives. A multinuclear nuclear magnetic resonance study

1988 ◽  
Vol 66 (9) ◽  
pp. 2443-2451 ◽  
Author(s):  
Philip A. W. Dean ◽  
Jagadese J. Vittal
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Nuclear Magnetic Resonance Study ◽  
Tetraalkylammonium Salts ◽  
Magnetic Resonance Study ◽  
Nmr Spectrum ◽  
Alternative Synthesis ◽  
H Nmr ◽  
Nmr Characterization

Multinuclear nmr (1H, 77Se, 111/113Cd, 119Sn, 199Hg, as appropriate) has been used to study Y−−EPh− exchange in Me2CO or MeCN between RnM′Y (RnM′ = Ph3Sn or MeHg; Y = Cl, Br, I, NCO, or NCS) and the adamantane-like anions [(μ-EPh)6(MEPh)4]2− (E = S, M = Zn, Cd, or Co; E = Se, M = Zn or Cd), as their tetraalkylammonium salts. Quantitative terminal substitution of the clusters occurs in most cases, giving [(μ-EPh)6(MEPh)4 − x(MY)x]2−(x = 1–4). However, reaction is incomplete for M = Cd, E = S or Se, RnM′Y = Ph3SnNCO or Ph3SnNCS and for M = Zn or Co, E = S, RnM′Y = MeHgI. Differences in the extents of reaction for Ph3SnY and MeHgY are consistent with the position of equilibrium in MeHgY:Ph3SnEPh mixtures.Group interchange provides a convenient alternative synthesis of the known halogen-substituted clusters [(μ-EPh)6(MY)4]2−(M = Zn or Cd, Y = Cl, Br, or I; M = Co, Y = Cl), and the first syntheses of [(μ-SPh)6(CoY)4]2− (Y = Br or I) and various pseudohalogen-substituted adamantanoid anions. The nuclei used for full direct nmr characterization of the new clusters in solution were: 77Se and 113Cd for [(μ-SePh)6(CdSePh)4 − x(CdY)x]2− (x = 1–4; Y = NCO or NCS); 77Se for [(μ-SePh)6(ZnSePh)4 − x(ZnY)x]2− (x = 1–4, Y = NCO or NCS); 113Cd for [(μ-SPh)6(CdSPh)4 − x(CdY)x]2−(x = 1–4; Y = NCO or NCS); 1H for [(μ-SPh)6(CoY)4]2− (Y = Br, I, NCO, or NCS). The first solution 1H nmr spectrum of [(μ-SPh)6(CoCl)4]2− is also reported.

Nuclear magnetic resonance study of complexes formed between conjugated Schiff bases and carboxylic acids

1994 ◽  
Vol 72 (11) ◽  
pp. 2220-2224
Author(s):  
H. Le-Thanh ◽  
D. Vocelle
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Carboxylic Acids ◽  
Nmr Spectra ◽  
Polar Solvent ◽  
Nuclear Magnetic Resonance Study ◽  
Magnetic Resonance Study ◽  
Natural Pigments ◽  
H Nmr ◽  
Rapid Proton ◽  
Tert Butylamine

The NMR spectra of the proton located in a N+---H---−O bond formed in the reaction of a conjugated Schiff base (SB) with a carboxylic acid (HA) in a non-polar solvent indicate that this proton is rapidly exchanging with other protons present in the system. For this study, two SB were used: all-trans-retinylidene tert-butylamine (RBA) and trans, tran-2,4-heptadienylidene tert-butylamine (HBA), and five carboxylic acids having pKa's between 0.66 and 4.87.1H NMR spectra were taken at 293 and 233 K in CDCl3 of systems of SB:HA using different ratios of acid to SB. Results indicate that the rapid proton exchanges are temperature and concentration dependent. Finally, the results are related to the natural pigments rhodopsin and bacteriorhodopsin.

Sesquiterpene alkaloids from Tripterygiumwilfordii (Hook): a nuclear magnetic resonance study of 1-desacetylwilfordine, 1-desacetylwilfortrine, and 2-debenzoyl-2-nicotinoylwilforine

1990 ◽  
Vol 68 (3) ◽  
pp. 371-374 ◽  
Author(s):  
Li Ya ◽  
George M. Strunz ◽  
Larry A. Calhoun
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Chemical Shift ◽  
Nmr Spectra ◽  
Nuclear Magnetic Resonance Study ◽  
Chemical Shift Assignments ◽  
Magnetic Resonance Study ◽  
Root Extracts ◽  
C Nmr ◽  
Nuclear Magnetic

1-Desacetylwilfordine, 8, 1-desacetylwilfortrine, 9, and 2-debenzoyl-2-nicotinoylwilforine, 10, have been isolated from root extracts of the Chinese medicinal and insecticidal plant Tripterygiumwilfordii. Analysis of the 1H and 13C NMR spectra of 8 and 10, with the aid of COSY, HCCOSY, and COLOC experiments, has allowed unambiguous chemical shift assignments of all protons and carbons of these alkaloids. Keywords: alkaloids, sesquiterpene, Celastraceae, Tripterygium, NMR.

Nuclear magnetic resonance studies. XXXI. Rearrangement and deuterium exchange through β-enolization in bicyclooctanones. An 2H nuclear magnetic resonance study.

1977 ◽  
Vol 55 (3) ◽  
pp. 447-453 ◽  
Author(s):  
A. K. Cheng ◽  
J. B. Stothers ◽  
C. T. Tan
Keyword(s):  
Nuclear Magnetic Resonance ◽  
Magnetic Resonance ◽  
Nuclear Magnetic Resonance Study ◽  
Magnetic Resonance Study ◽  
Deuterium Incorporation ◽  
Proton Abstraction ◽  
Magnetic Resonance Studies ◽  
H Nmr ◽  
Derivatives Of ◽  
Nuclear Magnetic

The bicyclo[2.2.2]octan-2-one and -[3.2.1]octan-6-one skeletons are interconvertible under strongly basic conditions. Their α,α-dimethyl derivatives in tert-Buo−/tert-BuOH at 185 °C undergo very slow interconversion by β-proton abstraction. Using 2H nmr the stereoselectivity of deuterium incorporation at the β-methylene sites was established. The relative reactivities of β-methyl exchange in the [3.2.1] system were also determined. As models for this process, exchange in the α,α,α′,α′-tetramethyl derivatives of the monocyclic ketones, C5–C8, was also studied.

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