Isotopic Studies of the Metal–Ligand Bond. Part II. The Far Infrared Spectra of Some Binuclear and Polymeric Copper Carboxylate Derivatives; Variable Temperature and Isotopic Studies of the Copper–Ligand Vibrations

1973 ◽  
Vol 51 (4) ◽  
pp. 514-519 ◽  
Author(s):  
A. B. P. Lever ◽  
B. S. Ramaswamy
Keyword(s):  
Infrared Spectra ◽  
Variable Temperature ◽  
Copper Acetate ◽  
Far Infrared ◽  
Dimeric Complexes ◽  
Isotopic Studies ◽  
Stretching Vibration ◽  
Amine Adducts ◽  
Far Infrared Spectra ◽  
Ligand Bond

The far infrared spectra of 16 adducts of pyridine, quinoline, isoquinoline, urea, aniline, o- and p-toluidine with copper acetate, propionate, and butyrate, and of copper formate tetrahydrate were recorded at ambient temperature and at −196 °C. A range of derivatives were prepared containing isotopically pure 65Cu. The spectra of these derivatives were used to identify, unequivocally, the copper–oxygen stretching frequencies.Complexes believed to be polymeric (aniline and toluidine adducts) exhibit one copper–oxygen stretching vibration between 300 and 350 cm−1 A second band, lying between 350 and 400 cm−1 is not isotopically sensitive. The dimeric complexes exhibit one or two bands in the 300–400 cm−1 region, all of which are isotopically sensitive. Certain of the amine adducts exhibit an isotopically sensitive band near 240 cm−1 assignable to a Cu—N stretching mode.

Isotopic Studies of the Metal–Ligand Bond. Part IV. Variable Temperature and Isotopic Studies of the Metal–Ligand Vibrations in Substituted Pyridine Metal Dihalides. Complexes of Cobalt(II), Nickel(II), and Copper(II)

1973 ◽  
Vol 51 (10) ◽  
pp. 1582-1586 ◽  
Author(s):  
A. B. P. Lever ◽  
Baratham S. Ramaswamy
Keyword(s):  
Low Temperature ◽  
Variable Temperature ◽  
Far Infrared ◽  
Isotopic Substitution ◽  
Isotopic Studies ◽  
Band Assignment ◽  
Derivatives Of ◽  
Far Infrared Spectra ◽  
Metal Ligand ◽  
Ligand Bond

The far infrared spectra (500–200 cm−1) of a series of picoline and ethylpyridine derivatives of cobalt(II), nickel(II), and copper(II) are reported. Metal–ligand assignments are based on isotopic substitution experiments with 65Cu and 62Ni. Low temperature data are also reported and it is noted that the energies of metal–ligand modes are much more sensitive to temperature than the energies of purely ligand vibrations. This observation is discussed and it is suggested, with some caution, that the low temperature behavior may be used as a guide to band assignment.

Hydrogen bonding in the gas phase: the thermodynamic properties of hydrogen fluoride-ether complexes and their far infrared spectra

1971 ◽  
Vol 322 (1548) ◽  
pp. 137-146 ◽  
Keyword(s):  
Hydrogen Bonding ◽  
Gas Phase ◽  
Infrared Spectra ◽  
Equilibrium Constants ◽  
Far Infrared ◽  
Methyl Ethyl ◽  
Rotational Contour ◽  
Stretching Vibration ◽  
Conformational Rearrangements ◽  
Far Infrared Spectra

The equilibrium constants of gas-phase complexes of HF with dimethyl, methyl ethyl and diethyl ether have been measured at several temperatures using the Benesi-Hildebrand approximation on the absorption band of the HF stretching vibration in the complex. From these, values of Δ H of — 43, — 38 and — 30 kJ mol -1 respectively, have been determined. They are interpreted in terms of conformational rearrangements of the ethers when they form hydrogen bonds. The far infrared spectra of the complexes with both HF and DF have also been recorded and in each case a band observed at around 180 cm -1 which is assigned to the intermolecular stretching mode of vibration. For the complex between HF and dimethyl ether a rotational contour has been observed at about 10 cm -1 .

Far infrared spectra of charge-transfer complexes between iodine and substituted pyridines

1967 ◽  
Vol 297 (1451) ◽  
pp. 440-448 ◽  
Keyword(s):  
Charge Transfer ◽  
Infrared Spectra ◽  
Equilibrium Constants ◽  
Far Infrared ◽  
Charge Transfer Complexes ◽  
Absorption Bands ◽  
Substituted Pyridines ◽  
Stretching Vibration ◽  
Far Infrared Spectra ◽  
Electronic And Steric Effects

Far infrared spectra of charge-transfer complexes between iodine and substituted pyridines, dissolved in cyclohexane, have been measured in the region 20 to 200 cm -1 . Bands have been assigned to the modified iodine molecule stretching vibration near 180 cm -1 , and to the stretching of the intermolecular bond in the range 65 to 95 cm -1 . The shifts of the vibration frequencies, and force constants calculated using a simple valency force field, have been discussed in relation to the mass, electronic and steric effects of substituent groups. Equilibrium constants for the formation of the complex have been determined. From the intensities of the absorption bands, further evidence has been found for a vibronic interaction, leading to a delocalization of the transition moment in the vibrations of the complexes, and to an enhancement of the intensity of absorption.

Isotopic Studies of the Metal–Ligand Bond. Part III. The Far Infrared Spectra of Some Tetragonal Diamine Complexes of Cobalt(II) and Nickel(II): Studies of the Metal–Nitrogen Bond, as a Function of Metal Ion and of Spin State

1973 ◽  
Vol 51 (10) ◽  
pp. 1567-1581 ◽  
Author(s):  
A. B. P. Lever ◽  
Elvio Mantovani
Keyword(s):  
Infrared Spectra ◽  
Metal Ion ◽  
Far Infrared ◽  
Geometric Factors ◽  
Square Planar ◽  
Isotopic Studies ◽  
First Time ◽  
Far Infrared Spectra ◽  
Metal Ligand ◽  
Nitrogen Bond

The far infrared spectra of 35 complexes of the formula M(diamine)2X2 are reported where M = Co(II) and Ni(II), X = Cl−, Br−, I−, NO3−, SCN−, ClO4−, and AgI2− and the diamine is ethylenediamine or its N,N-symmetric or antisymmetrically substituted dimethyl or diethyl derivative. Isotopic substitution studies with 62Ni and with 2H are carried out with eleven characteristic complexes and assignments for the metal–nitrogen modes in both octahedral and square planar complexes so deduced. In most cases the appropriate number of metal–ligand modes, based on symmetry considerations, are observed. The variations in observed M—N frequencies are discussed in terms of the electronic and geometric factors previously utilized for the corresponding copper(II) complexes. In complexes containing the asymmetric ligands, stretching vibrations arising from the two types of metal–nitrogen bond can be separately identified. Isotopic studies of pairs of complexes containing the same ligand and metal ion but with the latter in alternate spin states are reported here for the first time. All of the cobalt(II) complexes and several of the nickel(II) complexes are reported here for the first time.

Infrared spectra of hydrogen-bonded salicylic acid and its derivatives. Methyl salicylate

1983 ◽  
Vol 61 (7) ◽  
pp. 1449-1452 ◽  
Author(s):  
Marek J. Wójcik ◽  
Czesława Paluszkiewicz
Keyword(s):  
Infrared Spectra ◽  
Methyl Salicylate ◽  
Low Frequency ◽  
Far Infrared ◽  
Gaseous State ◽  
Stretching Vibration ◽  
Intramolecular Hydrogen ◽  
Solid Liquid ◽  
Far Infrared Spectra ◽  
Hydrogen Bonded

Infrared spectra of hydrogen-bonded methyl salicylate have been studied in the temperature range 173–293 K, in solutions of various concentrations (in CCl4) and in the gaseous state. Results show that the molecules form monomerie intramolecular hydrogen bonds in the solid, liquid, and gaseous state. Far-infrared spectra were recorded which give the wavenumber of low-frequency O … O mode used in theoretical reconstruction of the band connected with the O—H stretching vibration. The position and especially the width of this band are determined to a large extent by the influence of the environment.

Analysis of memory and nonadditivity effects on the far infrared spectra of HCl in rare gas liquids

1992 ◽  
Vol 54 (1-3) ◽  
pp. 67-72 ◽  
Author(s):  
A. Medina ◽  
A.Calvo Hernández ◽  
S. Velasco
Keyword(s):  
Infrared Spectra ◽  
Far Infrared ◽  
Rare Gas ◽  
Far Infrared Spectra

Far-infrared spectra of polycrystallineBa2YCu3O9−δ

1987 ◽  
Vol 36 (1) ◽  
pp. 846-849 ◽  
Author(s):  
G. A. Thomas ◽  
H. K. Ng ◽  
A. J. Millis ◽  
R. N. Bhatt ◽  
R. J. Cava ◽  
...  
Keyword(s):  
Infrared Spectra ◽  
Far Infrared ◽  
Far Infrared Spectra

Far-infrared spectra and structure of solid tellurium(IV) chloride, bromide, and iodide

1966 ◽  
pp. 1479 ◽  
Author(s):  
N. N. Greenwood ◽  
B. P. Straughan ◽  
Anne E. Wilson
Keyword(s):  
Infrared Spectra ◽  
Far Infrared ◽  
Far Infrared Spectra
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