Isotopic Studies of the Metal–Ligand Bond. Part I. Further Spectroscopic Studies of Copper Ethylenediamine Complexes: Copper–Nitrogen Vibrations

1972 ◽  
Vol 50 (23) ◽  
pp. 3866-3871 ◽  
Author(s):  
G. W. Rayner Canham ◽  
A. B. P. Lever
Keyword(s):  
Far Infrared ◽  
Spectroscopic Studies ◽  
Isotopic Substitution ◽  
Band Energy ◽  
Straight Line ◽  
Isotopic Studies ◽  
Metal Ligand ◽  
Ligand Bond

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.

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.

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.

Spectroscopic Review of the Normal Vibrations of Metal Complexes with Nitrogen-Containing Ligands

1968 ◽  
Vol 22 (6) ◽  
pp. 627-633 ◽  
Author(s):  
J. R. Durig ◽  
D. W. Wertz
Keyword(s):  
Metal Complexes ◽  
Molecular Nitrogen ◽  
Spectroscopic Studies ◽  
Normal Vibrations ◽  
Raman Spectroscopic ◽  
Ir And Raman ◽  
Metal Ligand ◽  
Ligand Bond

The ir and Raman spectroscopic studies of metal complexes with nitrogen-containing ligands have been reviewed. A special emphasis has been placed on the stretching and bending fundamentals of the metal—ligand bond. The following ligands are included in the discussion: nitrosyl, nitro, nitrite, nitride, azido, molecular nitrogen, hydrazine, isocyanate, isothiocyanate, isoselenocyanate, pyridine, and ethylenediamine.

Structural and spectroscopic studies of transition metal nitrite complexes. II. Crystal structures of cis-Bis(ethane-1,2-diamine)(nitrito-O,O')zinc(II) nitrite and trans-Bis[N,N-dimethyl(ethane-1,2-diamine)]dinitritozinc(II)

1981 ◽  
Vol 34 (10) ◽  
pp. 2061 ◽  
Author(s):  
AJ Finney ◽  
MA Hitchman ◽  
CL Raston ◽  
GL Rowbottom ◽  
AH White
Keyword(s):  
Transition Metal ◽  
Metal Ions ◽  
Crystal Structures ◽  
Coordination Polyhedron ◽  
Metal Ion ◽  
Spectroscopic Studies ◽  
Bond Lengths ◽  
Coordination Sites ◽  
Metal Ligand ◽  
Ligand Bond

The crystal structures of the complexes cis-bis(ethane-1,2-diamine)(nitrito-O,O')zinc(II) nitrite and trans-bis[N,N-dimethyl(ethane-l,2-diamine)]dinitritozinc(II) are described. The former compound contains one chelating nitrite, the second group being present as a counter ion. In this complex the coordination polyhedron about the metal ion may be described either as a distorted trigonal bi-pyramid or an octahedron, depending upon whether the chelated nitrite is considered to occupy one or two coordination sites. The second compound is a trans nitrito complex, having an octahedral ligand geometry, though with three markedly different metal-ligand bond lengths. The structures of the complexes are compared with those of analogous nickel(II) nitrite complexes, and the differences are discussed in terms of the electron configurations of the two metal ions.

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.

The Crystal and Molecular Structures of Two Modifications of cis-Dichloro-mer-tris-(dimethylphenylphosphine)hydridoiridium(III)

1988 ◽  
Vol 41 (3) ◽  
pp. 283 ◽  
Author(s):  
GB Robertson ◽  
PA Tucker
Keyword(s):  
Heavy Atom ◽  
Molecular Structures ◽  
Monoclinic Space Group ◽  
X Ray Diffraction ◽  
Orthorhombic Space Group ◽  
Space Group ◽  
X Ray ◽  
Bond Lengths ◽  
Metal Ligand ◽  
Ligand Bond

The structures of two crystalline modifications of mer -(Pme2Ph)3H-cis-Cl2IrIII, (1), have been determined from single-crystal X-ray diffraction data. Modification (A) is monoclinic, space group P21/c with a 12.635(1), b 30.605(3), c 14.992(2)Ǻ, β 110.01(2)° and Z = 8. Modification (B) is orthorhombic, space group Pbca with a 27.646(3), b 11.366(1), c 17.252(2)Ǻ and Z = 8. The structures were solved by conventional heavy atom techniques and refined by full-matrix least- squares analyses to conventional R values of 0.037 [(A), 8845 independent reflections] and 0.028 [(B), 5291 independent reflections]. Important bond lengths [Ǻ] are Ir -P(trans to Cl ) 2.249(1) av. (A) and 2.234(1) (B), Ir -P(trans to PMe2Ph) 2.339(2) av. (A) and 2.344(1), 2.352(1) (B), Ir-Cl (trans to H) 2.492(2), 2.518(2) (A) and 2.503(1) (B) and Ir-Cl (trans to PMe2Ph)2.452(2) av. (A) and 2.449(1)(B). Differences in chemically equivalent metal- ligand bond lengths emphasize the importance of non-bonded contacts in determining those lengths.

Metal Isotope Effect on Metal-Ligand Vibrations. IX. Far Infrared Spectra of Octahedral Nickel Halide Complexes of Pyridine and γ-Picoline

1973 ◽  
Vol 27 (3) ◽  
pp. 213-217 ◽  
Author(s):  
Y. Saito ◽  
C. W. Schläpfer ◽  
M. Cordes ◽  
K. Nakamoto
Keyword(s):  
Isotope Effect ◽  
Infrared Spectra ◽  
Far Infrared ◽  
Isotopic Shifts ◽  
Halide Complexes ◽  
Far Infrared Spectra ◽  
Metal Ligand

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.

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