Experimental (FT-IR and FT-RS) and theoretical (QC-DFT) studies of vibrational modes and molecular structure of new low-temperature phases of [Ru(NH3)6](BF4)3 and [Ru(NH3)6](ClO4)3

被引：5

作者：

Dolega, Diana ^{[1
]}

Mikuli, Edward ^{[1
]}

Chruszcz-Lipska, Katarzyna ^{[1
]}

机构：

[1] Jagiellonian Univ, Fac Chem, Dept Chem Phys, PL-30060 Krakow, Poland

来源：

SPECTROCHIMICA ACTA PART A-MOLECULAR AND BIOMOLECULAR SPECTROSCOPY | 2012年 / 98卷

关键词：

Ionic coordination compounds; Hexaammineruthenium(III) tetrafluoroborate and chlorate(VII); X-ray single crystal diffraction; Density functional theory; Potential energy distribution; Normal coordinate analysis; AB-INITIO; SCALING FACTORS; FREQUENCIES; EXCHANGE; SPECTRA; DRUGS;

D O I：

10.1016/j.saa.2012.08.021

中图分类号：

O433 [光谱学];

学科分类号：

0703 ; 070302 ;

摘要：

Vibrational spectra of [Ru(NH3)(6)](BF4)(3) and [Ru(NH3)(6)](ClO4)(3) in their novel low-temperature solid phases were recorded using FT-IR and FT-RS. Quantum chemical calculations of molecular structure and vibrational modes were made separately for BF4-, ClO4- and [Ru(NH3)(6)](3+) ions. The harmonic vibrational frequencies and the related IR and RS bands intensities and activities, respectively, were simulated at the B3LYP/6-311+G(d) and B3LYP/LANL2TZ(f)/6-311+G(d,p) levels of the DFT. Full interpretation of the vibrational spectra has been carried out with the aid of the normal coordinate analysis. The assignments of the vibrational modes were based on the potential energy distribution data, using the MOLVIB program. The calculated Ru-N stretching frequencies are too low, in comparison to experiment, which indicates that B3LYP method underestimates the Ru-N bond strength. Some values of calculated and measured (obtained from X-ray) bond lengths and angles were also compared. Conclusions about possible interactions inside and between the complex ions were drawn. (C) 2012 Elsevier B.V. All rights reserved.

引用

页码：132 / 141

页数：10

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