The rotational spectra of the molecular adducts concerning dimethylether (DME) show interesting features such as: (i) three weak C-H×××O improper H-bonds in the DME-DME dimer [1] and, (ii) the tunnelling splittings of Ar and Ne in the 1:1 complexes with DME [2,3]. Here we report the results of the studies on the interactions of DME with strong proton donors such as H2O, HF and HCl. All of them tunnel between the two lone pairs of the O atom of DME, generating huge inversion splittings in the rotational spectra. From them it has been possible to determine the rates and pathways of the inversion processes. . Millimeter wave absorption free jet and molecular beam Fourier transform microwave spectroscopy techniques have been used for the experiments.DME×××HCl is shown on the figure to the right. HCl is tunnelling from above to below the COC plane with a frequency of 8215.7 MHz. [1] – Y. Tatamitani, B. Liu, J. Shimada, T. Ogata, P. Ottaviani, A. Maris, W. Caminati and J. L. Alonso, J. Am. Chem. Soc., 124 (2002) 2739. [2] – P. Ottaviani, A. Maris, W. Caminati, Y. Tatamitani, Y. Suzuki, T. Ogata and J. L. Alonso, Chem. Phys. Letters, 361 (2002) 341. [3] – A. Maris and W. Caminati, J. Chem. Phys., 118 (2003) 1649.
W.Caminati, A.Maris, S.Melandri, A.Millemaggi, P.Ottaviani, B. Velino, et al. (2004). Protic Group Tunnelling in the 1:1 Complexes of Dimethylether with HF, HCl and H2O. s.l : s.n.
Protic Group Tunnelling in the 1:1 Complexes of Dimethylether with HF, HCl and H2O
CAMINATI, WALTHER;MARIS, ASSIMO;MELANDRI, SONIA;MILLEMAGGI, ALDO;OTTAVIANI, PAOLO;VELINO, BIAGIO;
2004
Abstract
The rotational spectra of the molecular adducts concerning dimethylether (DME) show interesting features such as: (i) three weak C-H×××O improper H-bonds in the DME-DME dimer [1] and, (ii) the tunnelling splittings of Ar and Ne in the 1:1 complexes with DME [2,3]. Here we report the results of the studies on the interactions of DME with strong proton donors such as H2O, HF and HCl. All of them tunnel between the two lone pairs of the O atom of DME, generating huge inversion splittings in the rotational spectra. From them it has been possible to determine the rates and pathways of the inversion processes. . Millimeter wave absorption free jet and molecular beam Fourier transform microwave spectroscopy techniques have been used for the experiments.DME×××HCl is shown on the figure to the right. HCl is tunnelling from above to below the COC plane with a frequency of 8215.7 MHz. [1] – Y. Tatamitani, B. Liu, J. Shimada, T. Ogata, P. Ottaviani, A. Maris, W. Caminati and J. L. Alonso, J. Am. Chem. Soc., 124 (2002) 2739. [2] – P. Ottaviani, A. Maris, W. Caminati, Y. Tatamitani, Y. Suzuki, T. Ogata and J. L. Alonso, Chem. Phys. Letters, 361 (2002) 341. [3] – A. Maris and W. Caminati, J. Chem. Phys., 118 (2003) 1649.I documenti in IRIS sono protetti da copyright e tutti i diritti sono riservati, salvo diversa indicazione.
