ChemInform Abstract: ISOTOPIC STUDIES OF THE METAL-LIGAND BOND PART 3, 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 4 (33) ◽  
pp. no-no
Author(s):  
A. B. P. LEVER ◽  
ELVIO MANTOVANI
1973 ◽  
Vol 51 (10) ◽  
pp. 1567-1581 ◽  
Author(s):  
A. B. P. Lever ◽  
Elvio Mantovani

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.


1973 ◽  
Vol 51 (4) ◽  
pp. 514-519 ◽  
Author(s):  
A. B. P. Lever ◽  
B. S. Ramaswamy

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.


1973 ◽  
Vol 51 (10) ◽  
pp. 1582-1586 ◽  
Author(s):  
A. B. P. Lever ◽  
Baratham S. Ramaswamy

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.


1973 ◽  
Vol 27 (3) ◽  
pp. 213-217 ◽  
Author(s):  
Y. Saito ◽  
C. W. Schläpfer ◽  
M. Cordes ◽  
K. Nakamoto

The far infrared spectra of Ni (pyridine)4X2 and Ni(γ-picoline)4X2 (X = CI, Br and I) have been measured. The Ni-X and Ni-N stretching bands have been assigned based on isotopic shifts due to the 58Ni-62Ni, pyridine-pyridine-d5, and Cl-37Cl substitutions.


FEBS Letters ◽  
1973 ◽  
Vol 30 (2) ◽  
pp. 199-204 ◽  
Author(s):  
V.T. Ivanov ◽  
G.A. Kogan ◽  
V.M. Tulchinsky ◽  
A.V. Miroshnikov ◽  
I.I. Mikhalyova ◽  
...  

1972 ◽  
Vol 50 (23) ◽  
pp. 3866-3871 ◽  
Author(s):  
G. W. Rayner Canham ◽  
A. B. P. Lever

Confirmation of the far infrared (500–200 K) spectroscopic assignments of the metal–ligand vibrations in the complexes Cu(N–N)2X2 and Cu(N–N)X2((N–N) = ethylenediamine, symmetric and asymmetric N,N-dimethyl- and N,N-diethylethylenediamine, X = Cl, Br, NO3) has been obtained from copper isotopic substitution measurements. Extension of the series Cu(ethylenediamine)2X2 has provided some exceptions to the straight line correlation between [v(Cu—N)]2 and mean electronic d–d band energy. These are discussed.


1975 ◽  
Vol 53 (2) ◽  
pp. 177-185 ◽  
Author(s):  
C. Preti ◽  
G. Tosi

Cobalt(II), nickel(II), copper(II), and copper(I) acetate, perchlorate, and tetrafluoroborate complexes with thiazolidine-2-thione, thiomorpholin-3-one, and thiomorpholin-3-thione have been prepared. On the basis of infrared and far infrared spectra, electronic spectroscopy, magnetism, and molecular conductance, the stereochemistries of these complexes were identified. Assignments for the metal–ligand modes have also been made. By the use of infrared spectroscopy it has been possible to distinguish whether or not the polyanions present in the complexes are coordinated to the transition metal ion or are present as free ions. Spectroscopic parameters for the complexes have been calculated and compared with similar chromophores containing sulfur, oxygen, and nitrogen donor atoms.


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