Phosphorus-31 and Mercury-199 N.M.R. studies on mercury(II) halidetributylphosphine complexes

1980 ◽  
Vol 33 (5) ◽  
pp. 955 ◽  
Author(s):  
R Colton ◽  
D Dakternieks
Keyword(s):  
Low Temperature ◽  
Time Scale ◽  
Slow Rate ◽  
Room Temperature ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Coupling Constant ◽  
Slowing Down ◽  
Halogen Exchange ◽  
And Shifts

Phosphorus-31 and mercury-199 N.M.R. studies have been carried out on HgX2P2,Hg2X4P2, mixtures thereof and the oligomers Hg2X4P3, Hg3X6P2 and Hg4X8P2 where X = Cl, Br, I and P = tributyl-phosphine. The results are consistent with exchange of both phosphine and halogen. The phosphine exchanges slowly on the N.M.R. time scale at room temperature, but rapidly on the preparative time scale. Halogen exchange is fast on both the N.M.R. and preparative time scales at room temperature; cooling to -120°C reduces exchange of terminal halogens to a slow rate on the n.m.r. time scale. Increase in the coupling constant JP,Hg at low temperature is attributed to the slowing down of halogen exchange. Exchange of bridging halogens is still fast at -120°C. ��� Mercury-199 chemical shifts span a range of over 3000 ppm and shifts have been correlated with 31P chemical shifts and with the coupling constants JP,Hg The 199Hg n.m.r. data confirm the existence of an asymmetrical isomer of Hg2I4(PBu3)2.

Phosphorus-31, cadmium-111, cadmium-113 and mercury-199 N.M.R. studies of cadmium(II) halide and mixed cadmium(II)-mercury(II) halide complexes with tributylphosphine

1980 ◽  
Vol 33 (8) ◽  
pp. 1677 ◽  
Author(s):  
R Colton ◽  
D Dakternieks
Keyword(s):  
Metal Complexes ◽  
Time Scale ◽  
Room Temperature ◽  
Chemical Shifts ◽  
Coupling Constant ◽  
Mixed Metal ◽  
Redistribution Reactions ◽  
Halide Complexes ◽  
Mixed Metal Complexes ◽  
And Shifts

Phosphorus-31, cadmium-111 and cadmium-113 n.m.r, studies have been carried out on CdX2(PBu3)2 (where X = Cl, Br, I). The results are consistent with exchange of both phosphine and halogen. Phosphine exchange becomes slow on the N.M.R. time scale in all cases by -40°C. Mixtures of CdX2(PBu3)2 with different halogens give averaged signals at room temperature, but below about -80°C exchange becomes slow and halogen redistribution reactions can be observed. ��� Reaction of CdX2 and PBu3 in 1 : 1 proportions in ethanol gives Cd2X4(PBu3)3 as the isolated product, not Cd2X4(PBu3)2. It is shown that ethanol is an effective ligand to cadmium and redistribution reactions between coordinated ethanol and the phosphine occur. ��� The mixed metal complexes CdHgX4(PBu3)2 have been shown by phosphorus-31, cadmium-113 and mercury-199 n.m.r, studies to have all the phosphine coordinated to mercury. ��� Cadmium-111 and cadmium-113 chemical shifts in these compounds span a range of over 500 ppm and shifts have been correlated with 31P chemical shifts and the coupling constant JP,Cd.

Carbon magnetic resonance studies of some phenyl, furyl and thienyl organometallics. Some comments on carbon-metal scalar coupling

1974 ◽  
Vol 27 (2) ◽  
pp. 417 ◽  
Author(s):  
D Doddrell ◽  
KG Lewis ◽  
CE Mulquiney ◽  
W Adcock ◽  
W Kitching ◽  
...  
Keyword(s):  
Chemical Shift ◽  
Chemical Shifts ◽  
Substituent Effects ◽  
Coupling Constants ◽  
Scalar Coupling ◽  
Coupling Constant ◽  
Aryl Substituent ◽  
Magnetic Resonance Studies ◽  
Thienyl Group ◽  
13C Chemical Shift

13C chemical shift variations within a series of phenyl, furyl and thienyl Group IVB organometallics appear to be best understood in terms of the usual alkyl and aryl substituent effects on 13C chemical shifts and not variations in dπ ?pπ metal-aryl interactions. Large changes in 13C-metal scalar coupling constants have been observed suggesting that other factors besides the s-character of the carbon-metal bond is responsible in determining the coupling constant.

Studies on the PMR Spectra of Oxetanes. VI 2-(3-Chlorophenyl)oxetane and 2-(2-Chlorophenyl)oxetane at 60 and 100 MHz

1974 ◽  
Vol 29 (12) ◽  
pp. 1902-1906 ◽  
Author(s):  
Jukka Jokisaari
Keyword(s):  
Long Range ◽  
Chemical Shifts ◽  
Methine Proton ◽  
Coupling Constants ◽  
Coupling Constant ◽  
Proton Proton ◽  
Temperature Range ◽  
Proton Coupling ◽  
Phenyl Proton ◽  
Pmr Spectra

The 100 MHz spectra of the phenyl protons in 2-(3-chlorophenyl) oxetane and 2-(2-chlorophenyl) oxetane have been analysed. The 60 MHz PMR chemical shifts and proton-proton coupling constants have been studied in the temperature range from -20 C to +80 °C. The chemical shifts were sensitive to temperature, while the coupling constants were not, except the long range 5Jm coupling constant between the methine proton and the meta positioned phenyl proton in 2-(2-chlorophenyl) oxetane.

13C and some 15N N.M.R. spectra of heteroaromatic molecules containing bridgehead nitrogen atoms

1980 ◽  
Vol 33 (3) ◽  
pp. 499 ◽  
Author(s):  
AJ Jones ◽  
P Hanisch ◽  
ML Heffernan ◽  
GM Irvine
Keyword(s):  
Electronic Structures ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Coupling Constant ◽  
Methyl Substitution ◽  
First Order ◽  
Degree Of Aromaticity ◽  
Bridgehead Nitrogen ◽  
High Degree ◽  
Free Pair

The carbon-13 and (in part) nitrogen-15 chemical shifts of 1,2,3- triazaindolizine and seven three ringed analogues of indolizine have been analysed and enable deductions to be made concerning the extent that the free pair of electrons on the bridgehead nitrogen atom contributes to the delocalized electronic structures. Analogies between these molecules and indolizine are noted in that all the systems possess a high degree of aromaticity. Additivity relationships for nitrogen and methyl substitution are compared with those previously reported for other heteroaromatic molecules. Comparison of previously published 100-MHz and the present-work 270-MHz proton n.m.r. results enabled 13C spectral assignments to be confirmed by selective 1H irradiation experiments, since coupling constant analyses did not provide unambiguous assignments in all cases. One-, two-, three- and four-bond 13C-1H coupling constants are reported for most carbon atoms where first-order spectral analysis was possible. Several examples of non-first-order behaviour are presented and attempts to reconcile the occurrence of this behaviour are outlined.

The Electric Field Gradient at the Site of the Halogen Ion and Structure of Amino Acid Hydrobromides and Hydroiodides

1992 ◽  
Vol 47 (7-8) ◽  
pp. 887-917
Author(s):  
Armin Kehrer ◽  
Shi-qi Dou ◽  
Alarieh Weiss
Keyword(s):  
Electric Field ◽  
Electric Field Gradient ◽  
Field Gradient ◽  
Room Temperature ◽  
Low Frequency ◽  
Coupling Constants ◽  
Coupling Constant ◽  
Resonance Frequencies ◽  
Quadrupole Coupling ◽  
Frequency Coupling

Abstract The 79,81Br and 127I NQR spectra of several hydrobromides, respectively hydroiodides, of amino acides and dipeptides were studied, mostly as functions of temperature in the range 77 < T/K <420. The investigated compounds are: L-Arg • HBr • H2O, L-Cys • HBr • H2O , L - Cys - S - S - L - Cys • 2HBr, ethanolamine • HBr, L-Glu • HBr, L-His • HBr, L-His • 2HBr, L-Ile HBr • H2O , Sar • HBr, (Sar)2 • HBr, L-Val • HBr • H2O , Gly • LiBr, Gly-Gly • LiBr, ethanolamine HI, Sar • HI, (Sar)2 • HI, (Gly)2 • HI, (L-Val)2 • HI, Gly-L-Leu • HI • H2O . A phase transition with hysteresis was observed for L-Val • HBr • H2O (Tc.up = 318 K, Tc.down = 242 K). Two solid phases of Sar • HI have been studied by NQR, one crystallized from melt, the other one from aqueous solution. For three of the title compounds the crystal structure was determined at room temperature: L-His - 2HBr, P212121 , Z = 4, aj pm = 1652, b/pm = 916, c/pm = 721; L-Cys HBr H2O , P212121 , Z = 4, a/pm = 1955, b/pm = 746, c/pm = 550; Gly-L-Leu • HI • H2O , P2X, Z = 2, a / p m = 1289, b/pm = 914, c/pm = 615, ß/° = 99.In most cases the halogen ion in the studied hydrohalides is polycoordinated by hydrogen bonds of the type N - H • • • X⊖ and O - H • • • X⊖ , X = Br, I. The NQR frequencies and, for iodine, the nuclear quadrupole coupling constants depend on this coordination. A low frequency (coupling constant) region is found for pure N - H • • • X⊖ coordination. Replacing one N - H • • • X⊖ bond by O - H • • • X⊖ rises the electric field gradient, EFG, respectively the resonance frequencies. The dependence of the EFG on the hydrogen bond coordination N - H • • • X⊖ plus O - H • • • X⊖ is discussed for the title compounds including information from literature

Lupin alkaloids 6. Stereochemistry of bis-quinolizidine alkaloids with γ-oxo-α,β-enamine system

1994 ◽  
Vol 72 (1) ◽  
pp. 193-199 ◽  
Author(s):  
Tadeusz Brukwicki ◽  
Waleria Wysocka ◽  
Barbara Nowak-Wydra
Keyword(s):  
Conformational Changes ◽  
Chemical Shifts ◽  
Molecular Geometry ◽  
Coupling Constants ◽  
Hydroxyl Group ◽  
Coupling Constant ◽  
H Nmr ◽  
Time Signals ◽  
Low Sensitivity ◽  
First Time

1H nmr, 1H,1H and 1H,13C COSY, and 2D J-resolved spectra of multiflorine (1) and 13α-hydroxymultiflorine (2) in CDCl3 were taken. Some erroneously determined chemical shifts in 1 were corrected and for the first time signals in 2 were assigned. Most of the coupling constants in 1 and 2 were established. A coupling constant of H7–H17β and chemical shifts for H17β, C14, and C8 were used to define the conformational equilibrium of boat or chair forms in the C rings, in 1 and 2 in solution. The results obtained confirm the previous findings based on chemical shifts of C12: ca. 75 and 70% of the "boat" conformer in 1 and 2, respectively, at room temperature. Of all the criteria used, the H7–H17β coupling constant seems to be least sensitive to the influence of substituents at rings A and D. From the Haasnoot equation, torsion angles of HCCH in regions of molecular geometry featuring low sensitivity to conformational changes were calculated. The hydroxyl group at position 13α has a slight influence on the geometry of ring D.

Phosphorus-31, mercury-199 and selenium-77 n.m.r. studies of ligand exchange reactions in mercury(II) halide complexes

1980 ◽  
Vol 33 (7) ◽  
pp. 1463 ◽  
Author(s):  
R Colton ◽  
D Dakternieks
Keyword(s):  
Time Scale ◽  
Ligand Exchange ◽  
Room Temperature ◽  
Mixed Ligand ◽  
Mixed Ligand Complexes ◽  
Exchange Reactions ◽  
Halogen Exchange ◽  
Redistribution Reactions ◽  
Halide Complexes

Mercury(II) halide complexes of tris(4-methoxyphenyl)phosphine have been investigated by 31P and 199Hg n.m.r. spectroscopy of CH2Cl2 solutions. At room temperature the phosphine exchanges at an appreciable rate and halogen exchange is fast. At -50°C both phosphine and halogen exchange are slow on the n.m.r. time scale and halogen redistribution reactions are observed. ��� Mercury(II) halide complexes with tributylphosphine selenide have been investigated by 31P, 199Hg and 77Se n.m.r. methods. This ligand is labile and exchanges rapidly on the n.m.r. time scale at room temperature, although the exchange can be slowed down at about -100°C. Halogen exchange is also fast at room temperature. ��� Ligand exchange reactions between tributylphosphine and either tris(4-methoxyphenyl)phosphine or tributylphosphine selenide were investigated and redistribution reactions to give mixed ligand complexes were observed.

Reconnaissance of diverse structural and electronic environments in germanium halides by solid-state 73Ge NMR and quantum chemical calculations

2011 ◽  
Vol 89 (9) ◽  
pp. 1118-1129 ◽  
Author(s):  
Brandon J. Greer ◽  
Vladimir K. Michaelis ◽  
Victor V. Terskikh ◽  
Scott Kroeker
Keyword(s):  
Solid State ◽  
Quantum Chemical Calculations ◽  
Quantum Chemical ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Coupling Constant ◽  
Electronic Environments ◽  
Isotropic Chemical Shifts ◽  
Spin Spin Coupling

Solid-state 73Ge nuclear magnetic resonance (NMR) is an attractive technique for the characterization of solid germanium-containing materials, but experiments can be exceedingly difficult in practice due to the unfavourable NMR properties of the 73Ge nucleus. Presented herein is a series of solid-state 73Ge NMR experiments on germanium halides (GeX4 and GeX2, where X = I, Br, and Cl) conducted at moderate (9.4 and 11.7 T) and ultrahigh (21.1 T) magnetic fields, intended to characterize the 73Ge NMR response in highly symmetric and asymmetric coordination environments. Quadrupole coupling constants range from 0.16 to 35 MHz. Isotropic chemical shifts for the GeX4 series trend with halide electronegativity, as found for the analogous silicon and tin halides. The indirect spin-spin coupling constant 1J(73Ge, 127I) is estimated from 73Ge MAS NMR to be 35 ± 10 Hz in GeI2, with the reduced coupling constant agreeing with those of other group 14 halides. Quantum chemical calculations using GIPAW DFT are in reasonable accord with experimental quadrupole couplings, but fail for chemical shielding. A preliminary NMR crystallographic study of GeI2 and GeCl2 incorporating 127I and 35Cl NMR spectra has led to plausible conclusions reflecting the structural homology of these compounds, although definitive characterization remains elusive.

An 1H NMR conformational analysis of 3-phenylpentane in solution

1993 ◽  
Vol 71 (4) ◽  
pp. 520-525 ◽  
Author(s):  
Ted Schaefer ◽  
Lina B.-L. Lee
Keyword(s):  
Alkyl Chain ◽  
Chemical Shifts ◽  
Close Approach ◽  
Solvent Mixture ◽  
Coupling Constants ◽  
Coupling Constant ◽  
Proton Proton ◽  
Vicinal Coupling Constants ◽  
Proton Coupling ◽  
Proton Chemical Shifts

Some 30 proton chemical shifts and proton–proton coupling constants are reported for a 4.7 mol% solution of 3-phenylpentane in a CS2/C6D12/TMS solvent mixture at 300 K. The long-range coupling constant over six formal bonds between the methine and para protons is used to deduce an apparent twofold barrier of 15.0 ± 0.3 kJ/mol to rotation about the Csp2—Csp3 bond, at least twice as large as that for isopropylbenzene in solution. AM1 computations agree with experiment in finding the conformation of lowest energy as that in which the methine C—H bond is situated in the phenyl plane, but predict a barrier height of only 13.9 kJ/mol. The vicinal coupling constants are consistent with a fractional population, 0.38(2), of the TT conformer, that in which all the carbon atoms of the alkyl chain lie in a plane. A doubly degenerate conformer, TG+(G−T), in which one methyl group is twisted away from the phenyl substituent, then has a fractional population of 0.62(2). The assumption that only these three conformers are present is tested with the signs and magnitudes of the four different coupling constants over four bonds. These coupling constants are consistent with the absence of significant proportions of the other six all-staggered conformers. These six are characterized by a close approach of the methyl groups (1,5 interactions) or by proximity of the methyl and phenyl moieties.

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