Abstract
Raman spectra taken at resonance with the eu(Br pπ) → b2g(Ru dπ) charge-transfer (CT) transition of the trans-[RuBr4(MeCN)2]– ion, as its [NBu4]+ salt at ca. 80 K, consist of long overtone progressions in ν1(a1g), the symmetric RuBr stretch (at 188.5 cm–1), together with combination band progressions in which ν1 is the progression-forming mode and the enabling modes include ν2(b1g), νas(RuBr), and ν4(b2g), δs(BrRuBr). The excitation profile of the ν1 band approximately follows the contour of the eu → b2g CT transition referred to above, consistent with the operation of the A-term scattering mechanism. The spectroscopic data allow the determination of the harmonic wavenumber (ω1) and anharmonicity (x11) of the ν1(a1g) mode to be 188.8 cm–1 and –0.15 cm–1, respectively. Some comparative data on the analogous chloride ion, trans-[RuCl4(MeCN)2]–, are also given.
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