Abstract: IR-vibrational absorption spectra of Co(III) ammine complexes [Co(NH3)5NO2]XY and [Co(NH3)5ONO]XY (XY=Cl2, Br2, I2, (NO3)2, Cl . NO3) were studied at static pressures up to 20 kbar in a diamond anvil cell. The shifts of valence (symmetric and asymmetric) and deformational frequencies of NO2-group were measured. Normal coordinate analysis of [Co(NH3)5NO2] and [Co(NH3)5ONO] models was carried out. The effect of kinematic factors on IR-vibrational frequencies was analyzed. The experimentally observed shifts of frequencies induced by pressure were interpreted on the basis of theoretical simulation of the spectra. The blue shift of both delta(NO2) and nu(as)(NO2) vibrational frequencies in the complexes with nitro (via nitrogen) coordination can be explained by a decrease in N-O bond lengths. The blue shift of nu(s)(ONO) and the red shift of nu(as)(ONO) frequencies in the complexes with nitrito (via oxygen) coordination can be explained by a decrease of the value of the O-N-O angle with increasing pressure. For comparison the pressure induced shifts of nu(s)(ONO) and nu(as)(ONO) for two Cr(III)-ammine complexes [Cr(NH3)5ONO]XY (XY=Cl2, were also measured. Whereas nu(s) behaves similar as in the corresponding Co-compounds, nu(as) is only slightly pressure dependent.

Cite: Boldyreva E.V. , Burgina E.B. , Baltachinov V.P. , Burleva L.P. , Ahsbahs H. , Uchtmann H. , Dulepov V.E.
Effect of High Pressure on the Infrared Spectra of Nitro- and Nitrito-Cobalt(III) Ammine Complexes
Сибирский химический журнал (В 1991г. переименовано из Известия Сибирского отделения Академии наук СССР). 1992. N3. P.104-115. WOS РИНЦ ANCAN

Identifiers:

Web of science:	WOS:A1992JL49000018
Elibrary:	47308676
Chemical Abstracts:	1992:580728
Chemical Abstracts (print):	117:180728

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