Bonding in d10 transition metal complexes. III. Infrared, Raman and N.Q.R. studies of some trimethylphosphine sulphide and trimethylarsine sulphide copper(I) complexes

1975 ◽  
Vol 28 (7) ◽  
pp. 1431 ◽  
Author(s):  
GA Bowmaker ◽  
R Whiting ◽  
EW Ainscough
Keyword(s):  
Transition Metal ◽  
Electric Field ◽  
Electric Field Gradient ◽  
Transition Metal Complexes ◽  
Infrared And Raman Spectra ◽  
Quadrupole Coupling ◽  
Orbital Mixing ◽  
Structure And Bonding ◽  
Nuclear Quadrupole ◽  
Bonding Scheme

The infrared, Raman and n.q.r. (63Cu, 65Cu) spectra of tris(trimethylphosphine sulphide)copper(I) perchlorate, [Cu(Me3PS)3] ClO4, cyclo-tris-μ(trimethylphosphine sulphide)-tri(chlorocopper(I)), (Me3PSCuCl)3, the trimethylarsine sulphide compounds [Cu(Me3AsS)3] ClO4, (Me3AsSCuCl)n (n = an integer), and the bromo and iodo compounds (Me3PSCuBr)n, (Me3PSCuI)n have been studied with the aim of finding out more about the structure and bonding in these complexes. The infrared and Raman spectra indicate that the trimethylarsine sulphide compounds are probably isostructural with the corresponding trimethylphosphine sulphide compounds. The origin of the electric field gradient responsible for the copper nuclear quadrupole coupling in these compounds is discussed, and it is shown that the copper n.q.r. results can be explained in terms of a bonding scheme involving 3d-4s orbital mixing.

Sternheimer Antishielding of the Fluorine Ion in Octahedral (MeF6)4-Complexes of Transition Metals from Perturbed Angular-Correlation Measurements

1977 ◽  
Vol 32 (10) ◽  
pp. 1119-1125 ◽  
Author(s):  
C. Bernhardt ◽  
F. W. Richter ◽  
D. Babel
Keyword(s):  
Transition Metal ◽  
Transition Metal Complexes ◽  
Axial Symmetry ◽  
Metal Ion ◽  
Perturbed Angular Correlation ◽  
Fluorine Nucleus ◽  
Quadrupole Coupling ◽  
Complexes Of Transition Metals ◽  
Nuclear Quadrupole ◽  
Antishielding Effect

Sternheimer antishielding factors of fluorine in octahedral transition metal complexes have been determined from nuclear quadrupole coupling data derived from differential perturbed angularcorrelation measurements taking into account ionic and covalent contributions to the electric field gradient at the fluorine nucleus. It has been found that the antishielding effect increases with increasing d-occupation in the metal ion, but is different for perovskite and rutile complexes and cannot be described by a scalar factor for the F--ions in rutile fluorides, where the fluor position is of less than axial symmetry

Nuclear Quadrupole Resonance of Antimony in Ln3Sb5O12 Crystals

1994 ◽  
Vol 49 (6) ◽  
pp. 687-689 ◽  
Author(s):  
A. M. Raevsky ◽  
A. G. Gukalova ◽  
G. K. Semin
Keyword(s):  
Electric Field ◽  
Electric Field Gradient ◽  
Coupling Constants ◽  
Spectral Parameters ◽  
Compression Effect ◽  
Quadrupole Coupling ◽  
Quadrupole Resonance ◽  
Nuclear Quadrupole ◽  
Asymmetry Parameters ◽  
Lanthanide Compression

Abstract Complete 121,123Sb NQR spectra of crystalline rate earth antimonites Ln3Sb5O12 (Ln = La, Nd, Er, Lu) were recorded at 77 K. The quadrupole coupling constants and asymmetry parameters of the electric field gradient were measured. A “lanthanide compression” effect on the antimony NQR was observed. Using relations found for the antimonites under study, the Sb spectral parameters of other lanthanide compounds can be predicted.

NUCLEAR ELECTRIC QUADRUPOLE INTERACTION IN SINGLE CRYSTALS

1952 ◽  
Vol 30 (3) ◽  
pp. 270-289 ◽  
Author(s):  
G. M. Volkoff ◽  
H. E. Petch ◽  
D. W. L. Smellie
Keyword(s):  
Electric Field ◽  
Electric Field Gradient ◽  
Field Gradient ◽  
Electric Quadrupole ◽  
Quadrupole Coupling Constant ◽  
Coupling Constant ◽  
Gradient Tensor ◽  
Absolute Value ◽  
Principal Axes ◽  
Quadrupole Coupling

Pound's theory of the dependence of electric quadrupole splitting of nuclear magnetic resonance absorption lines in a single crystal on the orientation of the crystal in an external magnetic field is extended to cover the case of a crystal with nonaxially symmetric electric field gradient at the site of the nuclei being investigated. It is shown that an experimental study of the angular dependence of this splitting for three independent rotations of the crystal about any three mutually perpendicular axes will yield complete information about the orientation of the principal axes and the degree of axial asymmetry of the electric field gradient tensor at the site of the nuclei, and also will give the absolute value of the quadrupole coupling constant for those nuclei.The authors' experiments on the splitting of the Li7 absorption lines in a single crystal of LiAl(SiO3)2 (spodumene) are described and are used to illustrate the theory. The absolute value of the quadrupole coupling constant for the Li7 nuclei in spodumene is found to be [Formula: see text]. per sec. The axial asymmetry parameter of the field gradient tensor at the site of the Li nuclei is found to be η≡(ϕxx−ϕvv)ϕzz=0.79 ± 0.01. One of the principal axes of this tensor (the y axis corresponding to the eigenvalue of intermediate magnitude) is experimentally found to coincide with the b crystallographic axis of monoclinic spodumene as required by the known symmetry of the crystal. The other two principal axes are in the ac plane, the z axis (corresponding to the eigenvalue ϕzz of greatest magnitude) lying between the a and c axes at an angle of 48° ± 2° with the c axis.

Ab initio Calculations of the Nuclear Quadrupole Coupling Constants of BHn = 2,4X+ (X = NH3, PH3, H2O, H2S)

2005 ◽  
Vol 60 (1-2) ◽  
pp. 37-40
Author(s):  
Tayyebe Partovi ◽  
Marjan A. Rafieea
Keyword(s):  
Electronic Structure ◽  
Electric Field Gradient ◽  
Coupling Constants ◽  
The Other ◽  
Quadrupolar Nuclei ◽  
Donor Atom ◽  
Acid Base ◽  
Donor And Acceptor ◽  
Quadrupole Coupling ◽  
Nuclear Quadrupole

The electronic structure and strength of acid-base bonding in the protonated boron-Lewis complexes BHn=2,4X+ (X = NH3, PH3, H2O, H2S) and their neutral parents were studied. The results showed that in the H2BX+ monocations the electron releasing from the donor atom in X to BH3 is significant and more complete than in the other studied complexes. Therefore the bonding between the donor and acceptor in H2BX+ is strongest. To obtain these data, the electric field gradient (EFG) at the quadrupolar nuclei in each complex was calculated. The EFG’s of the boron atom and other quadrupolar nuclei were calculated by the Gaussian 98 program, using the MP2/6-31G** method.

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