Experimental (IR, Raman) and Computational Analysis of a Series of PtBr 2 Derivatives: Vibrational Coupling in the Coordinated Ethylene and Pt−Br Modes - Archive ouverte HAL Accéder directement au contenu
Article Dans Une Revue Journal of Physical Chemistry A Année : 2009

Experimental (IR, Raman) and Computational Analysis of a Series of PtBr 2 Derivatives: Vibrational Coupling in the Coordinated Ethylene and Pt−Br Modes

Résumé

Compounds (nBu4P)[PtBr3(C2H4)] (1), trans-[PtBr2(NH2Ph)(C2H4)] (2), cis-[PtBr2(NH2Ph)(C2H4)] (3), (nPBu4)2[PtBr4] (4), (nPBu4)[PtBr3(NH2Ph)] (5), and cis-[PtBr2(NH2Ph)2] (6), as well as the trichlorido analogue of 1, (nBu4P)[PtCl3(C2H4)] (1Cl), have been investigated experimentally by both IR and Raman spectroscopy, and theoretically by geometry optimization and normal-mode analysis by the DFT approach. An analysis of the normal modes of coordinated ethylene in compounds 1, 1Cl, 2, and 3 followed by a potential energy distribution investigation shows extensive vibrational coupling between the ν(C═C) and δs(CH2) A1 modes in two bands at around 1510−1520 and 1230−1250 cm−1, the latter one having greater ν(C═C) contribution. The ρw(CH2) A1 mode, the contribution of which the above two bands is negligible, is responsible for a lower-frequency band at 995−1005 cm−1. A complete vibrational analysis, backed up by the DFT calculations, has also been carried out on the Pt−Br stretching vibrations of the tetrabromido complex 4, the tribromido complexes 1 and 5, and the dibromido complexes 2, 3, and 6, and on the Pt−Cl vibrations of the analogous complex 1Cl. The study illustrates the advantages of coupling high-level computations to the vibrational analyses to make unambiguous band assignments in IR and Raman spectroscopy.

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Chimie
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hal-03143334 , version 1 (29-03-2021)

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Pavel Dub, Oleg Filippov, Natalia Belkova, Mireia Rodriguez-Zubiri, Rinaldo Poli. Experimental (IR, Raman) and Computational Analysis of a Series of PtBr 2 Derivatives: Vibrational Coupling in the Coordinated Ethylene and Pt−Br Modes. Journal of Physical Chemistry A, 2009, 113 (22), pp.6348-6355. ⟨10.1021/jp902394j⟩. ⟨hal-03143334⟩
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