DETERMINATION OF COMPOSITION AND CONSTRUCTION OF COMPLEX COMPOUNDS OF TRANSITION METALS WITH DERIVATIVES OF AMINES BY METHOD OF IR-SPECTROSCOPIES

A. L. Kovalenko, T. A. Kizymishina

Abstract


Complex compounds of chloride and copper nitrate (II) with aliphatic amines R – NH2, R2 – NH, R3 – N, where R is C2H5; C3H5; C4H9; CH3(CH2)9; C5H11; and its substitutes from ethyl alcohol by merging solutions of copper (II) salts and amines in molecular ratios of 1:2, as well as complex compounds of copper (II) with N - derivatives of diethanolamine and benzyldiethylamine (RDEA), where R is C3H5; C3H7; C4H7 or C6thH5CH2, diethanolamine – NH (C2H4OH)2, are synthesized.

The absorption bands in the 440-420 cm-1 region, are identified which are related to ν (Cu – N) vibrations, that indicates about coordination through the nitrogen atom grounds. In the IR spectra of all complexes, an absorption band is observed in ligands in the region of 220-210 cm-1, which disappears in the complex. In the complexes there are bands of absorption in the region 460-430 cm-1, which are typical for copper (II) complexes with all amines and are practically independent of the amine radical.

The absorption frequencies of copper (II) complexes with benzyl, alliamines can be explained by the dual nature of σ- and π-dative interactions. In the low-frequency region of complexes of copper (II) halides with pyridine and its substituted an increase in the oscillation frequencies in the region 270-240 cm-1 is observed.

In the IR spectra of copper complexes with benzyldiethanolamines [Cu (BZDEA)2] X2 at interval 3500-3100 cm-1 two absorption bands appear. A band with a maximum at 3150 cm-1 probably refers to the absorption of coordinated OH groups. The coordination of the OH groups is confirmed by data in the absorption region v (C – 0), and also the appearance of the bands ν (Cu – O). The band of deformation vibrations of alcohol OH-groups at ~ 1650 cm-1 is shifted to the low-frequency region by 15 to 30 cm-1. It can be determined only by the interaction of hydroxy groups with cis.

Ligand is also coordinated through the nitrogen atom. This is confirmed by the pre-sence of absorption bands ν (Cu – N) in the region of 480-400 and 280-230 cm-1. Therefore, the ligand is tridentate.

Thus, according to the data of IR spectroscopy, molecules of N-derivatives diethanolamine form the bonds with c.y. through oxygen atoms of oxy groups. The fourth coordination site may be occupied by acid residues or the deprotonated oxygen atom of the hydroxy group performs a bridging function. Then the complex must have a dimeric or, in general, a polymeric structure.


Keywords


IR spectra; complexes; copper (II); aliphatic amines; pyridine; diethanolamine; benzyldiethanolamine

References


Beilsteins. Organische Chemie. Vol. IV – Berlin, 1921.

Климова В.А. Основные методы анализа органических соединений / В.А.Климова // – М.: Химия, 1975. – 224с.

Практическое руководство по неорганическому анализу / В.Ф.Гиллебранд, Г.Э.Лендель, Г.А.Брайт, Д.И.Гофман. – М.: Химия, 1966. – 1111с.

Шарло Г. Методы аналитической химии. Качественный анализ неорганических соединений. Ч.1 / Г.Шарло. – 2-е изд., исправл. и доп. – М.: Химия, 1969. – 667с.

Noji Masahide Studies of bivalent metal – chelates of 2 – aminomethylpyridine / Masahide Noji, Yoshinore Hidani, Hisashi Koike // Bull. Chem. Soc. Jud. – 1975. – Vol. 48, N1. – P.245-249.

Mahapatra B.K. Adduct of copper (II) bis (nitroacetyl – acetonata) with j – picoline / B.K.Mahapatra // Chemishe zvosti. – 1974. – Vol. 28, N6. – P.757-759.

Block H. A vibrational study of the hexamminecobalt (II) ion. / H.Block // Transaction of the Faraday Society. – 1959. – Vol. 55, №6. – P.867-875.

Powell D.B. The Infrared Spectra of Metallic Complexes. V. The Infrared Spectra of Nitro and Nitrito Complexes / D.B.Powell, N.Sheppard // Journal of the American Chemical Society. – 1958. – Vol. 80, N18. – P.4817-4823.

The infrared spectra and structure of complexes of copper (II) halides and heterocyclic bases / M.Goldstein, E.F.Mooney., A.Anderson, H.A.Gebbie // Spectrochimica Acta. – 1965. – Vol. 21, NI. – P.105-117.




DOI: https://doi.org/10.31319/2519-2884.33.2018.203

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Copyright (c) 2019 A. L. Kovalenko, T. A. Kizymishina

ISSN (print) 2519-2884

ISSN (online) 2617-8389