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Structural and Vibrational Properties of Silyl (SiH3–) Anions in KSiH3 and RbSiH3: New Insight into Si–H Interactions

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    Structural and Vibrational Properties of Silyl (SiH3–) Anions in KSiH3 and RbSiH3: New Insight into Si–H Interactions
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    † Department of Materials and Environmental Chemistry, Stockholm University, SE-10691 Stockholm, Sweden
    ‡ Department of Applied Physics, Chalmers University of Technology, SE-41296 Gothenburg, Sweden
    § Research Center of Natural Sciences, Hungarian Academy of Sciences, P.O. Box 77, H-1525, Budapest, Hungary
    ∥ Research Institute of Chemical and Process Engineering, Faculty of Information Technology, University of Pannonia, P.O. Box 158, H-8201 Veszprém, Hungary
    # Department of Chemical and Biological Engineering, Chalmers University of Technology, SE-41296 Gothenburg, Sweden
    *E-mail: [email protected]
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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2015, 54, 5, 2300–2309
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    https://doi.org/10.1021/ic502931e
    Published February 10, 2015
    Copyright © 2015 American Chemical Society
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    Abstract

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    The alkali metal silyl hydrides ASiH3 (A = K, Rb) and their deuteride analogues were prepared from the Zintl phases ASi. The crystal structures of ASiH3 consist of metal cations and pyramidal SiH3– ions. At room temperature SiH3– moieties are randomly oriented (α modifications). At temperatures below 200 K ASiH3 exist as ordered low-temperature (β) modifications. Structural and vibrational properties of SiH3– in ASiH3 were characterized by a combination of neutron total scattering experiments, infrared and Raman spectroscopy, as well as density functional theory calculations. In disordered α-ASiH3 SiH3– ions relate closely to freely rotating moieties with C3v symmetry (Si–H bond length = 1.52 Å; H–Si–H angle 92.2 °). Observed stretches and bends are at 1909/1903 cm–1 (ν1, A1), 1883/1872 cm–1 (ν3, E), 988/986 cm–1 (ν4, E), and 897/894 cm–1 (ν2, A1) for A = K/Rb. In ordered β-ASiH3 silyl anions are slightly distorted with respect to their ideal C3v symmetry. Compared to α-ASiH3 the molar volume is by about 15% smaller and the Si–H stretching force constant is reduced by 4%. These peculiarities are attributed to reorientational dynamics of SiH3– anions in α-ASiH3. Si–H stretching force constants for SiH3– moieties in various environments fall in a range from 1.9 to 2.05 N cm–1. These values are considerably smaller compared to silane, SiH4 (2.77 N cm–1). The reason for the drastic reduction of bond strength in SiH3– remains to be explored.

    Copyright © 2015 American Chemical Society

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    Supporting Information

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    PXRD patterns of α-KSiH3, α-KSiD3, α-RbSiH3, α-RbSiD3; Raman spectra of β-KSiH3, β-KSiD3, β-RbSiH3, β-RbSiD3; PDFs of α-KSiD3 and α-RbSiD3 at 200 K; observed IR and Raman bands for α-KSiH3 and α-RbSiH3; observed IR and Raman bands for α-KSiD3 and α-RbSiD3; details on force constant calculations and force constants for SiH3– in α-KSiH3 and α-RbSiH3; comparison of refined force constants for α- and β-ASiH3; comparison of experimental and calculated fundamental frequencies for SiH3– and SiD3– anions in β-ASiH3 and β-ASiD3; force constants for SiH4 and SiH62–; experimental and calculated fundamental vibrations for SiH4 and SiD4; experimental and calculated fundamental frequencies for SiH62–; stretching force constants for other SiHnν± species. This material is available free of charge via the Internet at http://pubs.acs.org.

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    Cited By

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    Inorganic Chemistry

    Cite this: Inorg. Chem. 2015, 54, 5, 2300–2309
    Click to copy citationCitation copied!
    https://doi.org/10.1021/ic502931e
    Published February 10, 2015
    Copyright © 2015 American Chemical Society
    Request reuse permissions

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