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Issue 45, 2011
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Vibrations of a chelated proton in a protonated tertiary diamine

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Vibrational spectra of the conjugate acid of Me2NCH2CH2CH2CH2NMe2 (N,N,N′,N′-tetramethylputrescine) have been examined in the gaseous and crystalline phases using Infrared Multiple Photon Dissociation (IRMPD) spectroscopy, Inelastic Neutron Scattering (INS), and high pressure Raman spectroscopy. A band observed near 530 cm−1 is assigned to the asymmetric stretch of the bridging proton between the two nitrogens, based on deuterium substitution and pressure dependence. The NN distance measured by X-ray crystallography gives a good match to DFT calculations, and the experimental band position agrees with the value predicted from theory using a 2-dimensional potential energy surface. The reduced dimensionality potential energy surface, which treats the ion as though it possesses a linear NHN geometry, shows low barriers to proton transit from one nitrogen to the other, with zero point levels close to the barrier tops. In contrast, two other related systems containing strong hydrogen bonds do not exhibit the same spectroscopic signature of a low barrier hydrogen bond (LBHB). On the one hand, the IRMPD spectra of the conjugate acid ions of the amino acidN,N,N′,N′-tetramethylornithine (in which the two nitrogens have different basicities) show fewer bands and no comparable isotopic shifts in the low frequency domain. On the other hand, the IRMPD spectrum of the shorter homologue Me2NCH2CH2CH2NMe2 (N,N,N′,N′-tetramethyl-1,3-propanediamine), for which the NHN bond angle deviates substantially from linearity, displays more than one band in the 1100–1400 cm−1 domain, which vanish as a consequence of deuteration.

Graphical abstract: Vibrations of a chelated proton in a protonated tertiary diamine

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The article was received on 24 Jun 2011, accepted on 19 Sep 2011 and first published on 13 Oct 2011

Article type: Paper
DOI: 10.1039/C1CP22065A
Phys. Chem. Chem. Phys., 2011,13, 20380-20392

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    Vibrations of a chelated proton in a protonated tertiary diamine

    G. J. O. Beran, E. L. Chronister, L. L. Daemen, A. R. Moehlig, L. J. Mueller, J. Oomens, A. Rice, D. R. Santiago-Dieppa, F. S. Tham, K. Theel, S. Yaghmaei and T. H. Morton, Phys. Chem. Chem. Phys., 2011, 13, 20380
    DOI: 10.1039/C1CP22065A

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