title: Conformational properties of 1-silyl-1-silacyclohexane, C(5)H(10)SiHSiH(3): gas electron diffraction, low-temperature NMR, temperature-dependent Raman spectroscopy, and quantum chemical calculations (&).
abstract: The molecular structure of axial and equatorial conformers of 1-silyl-silacyclohexane, C(5)H(10)SiHSiH(3), and the thermodynamic equilibrium between these species were investigated by means of gas electron diffraction (GED), dynamic nuclear magnetic resonance (DNMR), temperature-dependent Raman spectroscopy, and quantum chemical calculations (CCSD(T), MP2 and DFT methods). According to GED, the compound exists as a mixture of two conformers possessing the chair conformation of the six-membered ring and C(s) symmetry and differing in the axial or equatorial position of the SiH(3) group (axial = 57(7) mol %/equatorial = 43(7) mol %) at T = 321 K. This corresponds to an A value (free energy difference = G(axial) - G(equatorial)) of -0.17(15) kcal mol(-1). A low-temperature (13)C NMR experiment using SiD(4) as a solvent resulted in an axial/equatorial ratio of 45(3)/55(3) mol % at 110 K corresponding to an A value of 0.05(3) kcal mol(-1), and a DeltaG(#) value of 5.7(2) kcal mol(-1) was found at 124 K. Temperature-dependent Raman spectroscopy in the temperature range of 210-300 K of the neat liquid, a THF solution, and a heptane solution indicates that the axial conformer is favored over the equatorial one by 0.26(10), 0.23(10), and 0.22(10) kcal mol(-1) (DeltaH values), respectively. CCSD(T)/CBS and MP2/CBS calculations in general predict both conformations to have very similar stability and are, thus, in excellent agreement with the DNMR result but in a slight disagreement with the GED and Raman results. Two DFT functionals, that account for dispersion interactions, M06-2X/pc-3 and B2PLYP-D/QZVPP, deviate from the high-level coupled cluster and MP2 calculations by only 0.1 kcal mol(-1) on average, whereas B3LYP/pc-3 calculations greatly overestimate the stability of the equatorial conformer.
authors.affiliation: Science Institute, University of Iceland, Dunhaga 3, IS-107 Reykjavik, Iceland.
authors.forename: Sunna O
authors.initials: SO
authors.lastname: Wallevik
authors.forename: Ragnar
authors.initials: R
authors.lastname: Bjornsson
authors.forename: Agúst
authors.initials: A
authors.lastname: Kvaran
authors.forename: Sigridur
authors.initials: S
authors.lastname: Jonsdottir
authors.forename: Ingvar
authors.initials: I
authors.lastname: Arnason
authors.forename: Alexander V
authors.initials: AV
authors.lastname: Belyakov
authors.forename: Alexander A
authors.initials: AA
authors.lastname: Baskakov
authors.forename: Karl
authors.initials: K
authors.lastname: Hassler
authors.forename: Heinz
authors.initials: H
authors.lastname: Oberhammer
mesh_terms: D003198:Computer Simulation; D004583:Electrons; D005740:Gases / Q000737:chemistry; D009682:Magnetic Resonance Spectroscopy; D008956:Models, Chemical; D008968:Molecular Conformation; D017646:Organosilicon Compounds / Q000737:chemistry*; D011789:Quantum Theory; D013059:Spectrum Analysis, Raman; D013696:Temperature; D013816:Thermodynamics
chemical_list: C549103:1-silyl-1-silacyclohexane; D005740:Gases; D017646:Organosilicon Compounds