Solid-state nuclear magnetic resonance studies of triphenylsilyl-, triphenyltin-, and triphenyllead(pentacarbonyl)manganese(I) complexes

1999 ◽  
Vol 77 (11) ◽  
pp. 1892-1898 ◽  
Author(s):  
Dharamdat Christendat ◽  
Ian S Butler ◽  
Denis FR Gilson ◽  
Frederick G Morin
Keyword(s):  
Solid State ◽  
Chemical Shift ◽  
Dipolar Coupling ◽  
Chemical Shifts ◽  
Chemical Shift Anisotropy ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Chemical Shift Tensors ◽  
Lead Compounds ◽  
Spin Spin Coupling

The solid-state CP MAS (29Si, 119Sn, and 207Pb) NMR spectra of the triphenylsilyl-, triphenyltin-, and triphenyllead(pentacarbonyl)manganese(I) complexes, (Ph3E)Mn(CO)5 (E = Si, Sn, Pb), have been analyzed to give the chemical shifts, one-bond spin-spin coupling constants, 1JE-Mn, the "effective-dipolar" coupling constants (D - ΔJ/3), the chemical shift tensors, and the spin-spin anisotropy (ΔJ), where the analysis permits. For the tin and lead compounds, three and four sets of chemical shifts, respectively, were observed, and two different polymorphs occur for the lead complex, depending on the solvent used for recrystallization. The average values of the reduced coupling constants, 1KMn-Si (2.64 × 1020 T2 J-1), 1KSn-Mn (1.25 × 1020 T2 J-1), and 1KPb-Mn (4.18 × 1020 T2 J-1) showed a linear correlation with the s-electron densities at the respective metal nuclei. The principal components of the chemical shift tensors have been determined for the tin and lead compounds.Key words: manganese-group-14 compounds, solid-state 29Si, 119Sn, and 207Pb CP MAS NMR, spin-spin coupling, chemical shift anisotropy, quadrupole coupling.

9-Borafluorenes – NMR spectroscopy and DFT calculations. Molecular structure of 1,2-(2,2′-diphenylylene)-1,2-diethyldiborane

2010 ◽  
Vol 75 (7) ◽  
pp. 743-756 ◽  
Author(s):  
Bernd Wrackmeyer ◽  
Peter Thoma ◽  
Rhett Kempe ◽  
Germund Glatz
Keyword(s):  
Molecular Structure ◽  
Nmr Spectroscopy ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Spin Coupling ◽  
X Ray Diffraction ◽  
Data Set ◽  
Chemical Shift Tensors ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling

9-Borafluorene derivatives 1 (9-R = Et (a), Ph (b), Cl (c), NEt2 (d)), the pyridine adduct 1py+ and 1,2-(2,2′-biphenylylene)-1,2-diethyldiborane(6) (3), were studied by 11B and 13C NMR spectroscopy to obtain a fairly complete data set for the first time. The molecular structure of the doubly hydrogen-bridged 1,2-diphenylenediborane 3 was determined by X-ray diffraction. The gas-phase structures of the compounds 1, related derivatives, and of some doubly hydrogen-bridged 1,2-diphenylenediboranes were optimized by quantum chemical calculations (B3LYP/6-311+G(d,p) level of theory) and NMR parameters, such as chemical shifts, 11B chemical shift tensors and indirect nuclear 13C–11B spin–spin coupling constants were calculated at the same level of theory and compared with experimental data.

Characterization of indirect 31P-31P spin-spin coupling and phosphorus chemical shift tensors in pentaphenylphosphinophosphonium tetrachlorogallate, [Ph3P-PPh2][GaCl4]

2002 ◽  
Vol 80 (11) ◽  
pp. 1488-1500 ◽  
Author(s):  
Myrlene Gee ◽  
Roderick E Wasylishen ◽  
Paul J Ragogna ◽  
Neil Burford ◽  
Robert McDonald
Keyword(s):  
Chemical Shift ◽  
Density Functional ◽  
Dipolar Coupling ◽  
Spin Coupling ◽  
Coupling Constant ◽  
Chemical Shift Tensors ◽  
Self Consistent Field ◽  
Self Consistent Field Theory ◽  
Spin Spin Coupling ◽  
Phosphorus Nucleus

Phosphorus chemical shift and 31P,31P spin-spin coupling tensors have been characterized for pentaphenylphosphinophosphonium tetrachlorogallate, [Ph3P-PPh2][GaCl4], using solid-state 31P NMR spectroscopy. Spectra obtained with magic-angle spinning yield the isotropic value of the indirect spin-spin coupling, |1J(31P,31P)iso|, 323 ± 2 Hz, while 2D spin-echo and rotational resonance experiments provide the effective dipolar coupling constant, Reff, 1.70 ± 0.02 kHz, and demonstrate that Jiso is negative. Within experimental error, the effective dipolar coupling constant and Jiso are unchanged at –120°C. The anisotropy in 1J(31P,31P), ΔJ, has been estimated by comparison of Reff and the value of the dipolar coupling constant, RDD, calculated from the P—P bond length as determined by X-ray diffraction. It is concluded that |ΔJ| is small, with an upper limit of 300 Hz. Calculations of 1J(31P,31P) for model systems H3P-PH+2 and (CH3)3P-P(CH3)+2 using density functional theory as well as multiconfigurational self-consistent field theory (H3P-PH+2) support this conclusion. The experimental spin-spin coupling parameters were used to analyze the 31P NMR spectrum of a stationary powder sample and provide information about the phosphorus chemical shift tensors. The principal components of the phosphorus chemical shift tensor for the phosphorus nucleus bonded to three phenyl groups are δ11 = 36 ppm, δ22 = 23 ppm, and δ33 = –14 ppm with an experimental error of ±2 ppm for each component. The components are oriented such that δ33 is approximately perpendicular to the P—P bond while δ11 forms an angle of 31° with the P—P bond. For the phosphorus nucleus bonded to two phenyl groups, the principal components of the phosphorus chemical shift tensor are δ11 = 23 ppm, δ22 = –8 ppm, and δ33 = –68 ppm with experimental errors of ±2 ppm. In this case, δ33 is also approximately perpendicular to the P—P bond; however, δ22 is close to the P—P bond for this phosphorus nucleus, forming an angle of 13°. The dihedral angle between the δ33 components of the two phosphorus chemical shift tensors is 25°. Results from ab initio calculations are in good agreement with experiment and suggest orientations of the phosphorus chemical shift tensors in the molecular frame of reference.Key words: Nuclear magnetic resonance spectroscopy, phosphorus chemical shift tensors, 31P-31P J-coupling tensors, density functional theory, multiconfigurational self-consistent field theory, phosphinophosphonium salts.

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.

31P chemical shift anisotropies of trimethyl- and triphenylphosphine-substituted Group 6 metal pentacarbonyl complexes

1998 ◽  
Vol 76 (9) ◽  
pp. 1280-1283 ◽  
Author(s):  
Jordan H Wosnick ◽  
Frederick G Morin ◽  
Denis FR Gilson
Keyword(s):  
Chemical Shift ◽  
Reasonable Agreement ◽  
Chemical Shifts ◽  
Chemical Shift Anisotropy ◽  
Coupling Constants ◽  
Torsion Angles ◽  
Chemical Shift Tensors ◽  
Group 6 ◽  
Phenyl Rings ◽  
The One

The 31P chemical shift tensor components and anisotropies of the trimethyl- and triphenylphosphine complexes of the group 6 metal pentacarbonyls, M(CO)5PR3 (M = Cr, Mo, W and R = Me, Ph), have been measured using solid-state CP-MAS 31P NMR spectroscopy. For the trimethylphosphine derivatives, the chemical shift tensors have near axial symmetry and the shift tensor components are in reasonable agreement with the calculated values for the chromium and molybdenum complexes. In the triphenylphosphine complexes, the tensors are asymmetric due to the different torsion angles of the phenyl rings. The trend to higher shielding of the isotropic 31P chemical shifts on descending group 6 arises from changes in the perpendicular components of the shift tensor. The one-bond coupling constants, 1J(95/97Mo-31P), for the trimethyl- and triphenylphosphine complexes are 129 and 133 Hz, respectively.Key words: chemical shift anisotropy, phosphines, chromium, molybdenum, tungsten.

Structural Characterization of Natural Products By Means of Quantum Chemical Calculations of NMR Parameters: New insights

2021 ◽  
Author(s):  
Fabio Luiz Paranhos Costa ◽  
Ana Carolina Ferreira de Albuquerque ◽  
Rodolfo Goetze Fiorot ◽  
Luciano Morais Lião ◽  
Lucas Haidar Martorano ◽  
...  
Keyword(s):  
Natural Products ◽  
Structural Characterization ◽  
Quantum Chemical ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Nmr Parameters ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling

The calculation of NMR parameters for natural products was pioneered by Bifulco and coworkers in 2002. Since then, modelling 1H and 13C chemical shifts and spin-spin coupling constants for this...

Are the amide bonds in N-acyl imidazoles twisted? A combined solid-state 17O NMR, crystallographic, and computational study

2015 ◽  
Vol 93 (4) ◽  
pp. 451-458 ◽  
Author(s):  
Xianqi Kong ◽  
Aaron Tang ◽  
Ruiyao Wang ◽  
Eric Ye ◽  
Victor Terskikh ◽  
...  
Keyword(s):  
Solid State ◽  
Chemical Shift ◽  
Crystal Structures ◽  
Computational Study ◽  
Chemical Shifts ◽  
Amide Bond ◽  
Chemical Shift Tensors ◽  
Amide Bonds ◽  
Bond Rotation ◽  
Quadrupole Coupling

We report synthesis of 17O-labeling and solid-state 17O NMR measurements of three N-acyl imidazoles of the type R-C(17O)-Im: R = p-methoxycinnamoyl (MCA-Im), R = 4-(dimethylamino)benzoyl (DAB-Im), and R = 2,4,6-trimethylbenzoyl (TMB-Im). Solid-state 17O NMR experiments allowed us to determine for the first time the 17O quadrupole coupling and chemical shift tensors in this class of organic compounds. We also determined the crystal structures of these compounds using single-crystal X-ray diffraction. The crystal structures show that, while the C(O)–N amide bond in DAB-Im exhibits a small twist, those in MCA-Im and TMB-Im are essentially planar. We found that, in these N-acyl imidazoles, the 17O quadrupole coupling and chemical shift tensors depend critically on the torsion angle between the conjugated acyl group and the C(O)–N amide plane. The computational results from a plane-wave DFT approach, which takes into consideration the entire crystal lattice, are in excellent agreement with the experimental solid-state 17O NMR results. Quantum chemical computations also show that the dependence of 17O NMR parameters on the Ar–C(O) bond rotation is very similar to that previously observed for the C(O)–N bond rotation in twisted amides. We conclude that one should be cautious in linking the observed NMR chemical shifts only to the twist of the C(O)–N amide bond.

The planar conformation of 2-methylthiobenzaldehyde in solution

1983 ◽  
Vol 61 (1) ◽  
pp. 26-28
Author(s):  
Ted Schaefer ◽  
Rudy Sebastian
Keyword(s):  
Chemical Shifts ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Spectral Parameters ◽  
H Nmr ◽  
Heavy Atoms ◽  
Planar Conformation ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling ◽  
Infrared Data

The 1H nmr spectral parameters are extracted for a 4 mol% solution of 2-methylthiobenzaldehyde in CCl4 at 305 K. The long-range spin–spin coupling constants involving the aldehydic and methyl protons are consistent only with a preferred conformation in which all heavy atoms are coplanar, as are the chemical shifts of the ring and methyl protons. This conclusion contradicts previous interpretations of the dipole moment, the nmr parameters, and of the infrared data for CCl4 solutions. The present data show that the O-syn and O-anti forms of the compound are present in roughly equal proportions.

A Comparative Study of Metal Shielding in Low Valent Vanadium, Niobium and Manganese Complexes

1982 ◽  
Vol 37 (5) ◽  
pp. 631-645 ◽  
Author(s):  
Dieter Rehder ◽  
Hans-Christoph Bechthold ◽  
Ahmet Keçeci ◽  
Hartwig Schmidt ◽  
Michael Siewing
Keyword(s):  
Comparative Study ◽  
Nuclear Spin ◽  
Chemical Shifts ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Manganese Complexes ◽  
Ligand Field ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling ◽  
Ligand Bond

Variations of the metal chemical shifts δ(51V), δ(55Mn) and δ(93Nb) with the paramagnetic deshielding contribution to the overall shielding are discussed in terms of influences imposed by the ligand field splitting, the nephelauxetic effect and the covalency of the metal-to-ligand bond. Complexes under investigation are isoelectronic and/or iso-structural series [M(CO)6-nLn]q (M = V, Nb: q = -1; M = Mn: q = + 1; n = 0-6), η5-C5H5M(CO)4-nLn (M = V, Nb; n = 0-4) and η5-C5H5M(L')2L (M = V, L' = NO; M = Mn, L' = CO). L is a monodentate or l/n oligodentate phosphine. η varies with the point symmetry of the complex, and with ligand parameters of primarily electronic or steric origin. Generally, for weak to medium π-interaction, there is a decrease of shielding with decreasing π-acceptor power of the ligand, increasing ligand bulkiness, increasing ring strains in chelate structures and increasing degree of substitution. For strong π-interaction, the trends may be interconverted. PF3 is shown to be a slightly weaker π-acceptor than CO. Selected results on nuclear-spin spin coupling constants, 13C and 31P shielding are also presented

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