Radical recombination has been proposed to lead to the formation of complex organic molecules (COMs) in CO-rich ices in the early stages of star formation. These COMs can then undergo hydrogen addition and abstraction reactions leading to a higher or lower degree of saturation. Here, we have studied 14 hydrogen transfer reactions for the molecules glyoxal, glycoaldehyde, ethylene glycol, and methylformate and an additional three reactions where CH n O fragments are involved. Over-the-barrier reactions are possible only if tunneling is invoked in the description at low temperature. Therefore the rate constants for the studied reactions are calculated using instanton theory that takes quantum effects into account inherently. The reactions were characterized in the gas phase, but this is expected to yield meaningful results for CO-rich ices due to the minimal alteration of reaction landscapes by the CO molecules.We found that rate constants should not be extrapolated based on the height of the barrier alone, since the shape of the barrier plays an increasingly larger role at decreasing temperature. It is neither possible to predict rate constants based only on considering the type of reaction, the specific reactants and functional groups play a crucial role. Within a single molecule, though, hydrogen abstraction from an aldehyde group seems to be always faster than hydrogen addition to the same carbon atom. Reactions that involve heavy-atom tunneling, e.g., breaking or forming a C-C or C-O bond, have rate constants that are much lower than those where H transfer is involved.
The new rare‐earth metal(III) oxotellurates(IV) RE2Te3O9 (RE=La−Nd) of the so far unknown A‐type structure can be obtained as needle‐shaped single crystals through solid‐state reactions of the corresponding binary oxides. Their crystal structures were determined as A1‐type for RE=La and Ce or A2‐type for RE=Pr and Nd by single‐crystal X‐ray diffraction. Both structure types crystallize in the monoclinic crystal system, but in two different non‐centrosymmetric space groups: the A1‐type with Z=8 in space group P21 (La2Te3O9: a=569.54(3), b=2230.12(13), c=1464.71(4) pm, β=101.205(3)°; Ce2Te3O9: a=567.02(3), b=2222.61(13), c=1457.13(9) pm, β=101.134(3)°) or the A2‐type with Z=16 in space group Cc (Pr2Te3O9: a=2838.61(16), b=563.89(3), c=2522.08(15) pm, β=118.816(3)°; Nd2Te3O9: a=2826.38(16), b=561.47(3), c=2511.94(15) pm, β=118.841(3)°). In spite of the differences in the unit‐cell parameters and the symmetry, both structures consist of quite similar fundamental building blocks (FBBs) consisting of eight crystallographically distinct rare‐earth metal‐oxygen polyhedra with C.N.(RE3+) from seven to nine and always twelve different ψ1‐tetrahedral oxotellurate(IV) anions [TeO3]2−, which show a high number of secondary bonding interactions (SBIs) with each other in all four cases.
The two new scandium oxotellurates(IV) Sc2Te3O9 and Sc2Te4O11 were synthesized through firing appropriate mixtures of Sc2O3, TeO2 and CsBr (as flux) in evacuated glassy silica ampoules at 850 °C for 10 days. Both of them crystallize in the monoclinic space group P21/c with Z = 4 (Sc2Te3O9: a = 523.36(3), b = 2438.23(14), c = 731.98(4) pm, β = 116.221(3)°; Sc2Te4O11: a = 949.51(6), b = 779.12(5), c = 1341.93(9) pm, β = 90.829(3)°). Both crystal structures contain two crystallographically unique Sc3+ cations. In the case of Sc2Te3O9, they reside in six- and sevenfold oxygen coordination arranged as distorted uncapped or capped octahedra, while for Sc2Te4O11, they only exhibit six oxygen atoms in the coordination polyhedra, but one of them has also a certain tendency to thrive for a higher coordination number (C.N. = 6 + 1). The [(Sc1)O6)]9− and [(Sc2)O6+1)]11− polyhedra in Sc2Te3O9 are condensed via common edges to form serrated ∞ 1 { [ Sc 2 O 6 / 1 t O 1 / 2 v O 4 / 2 e ] 11 − } ${\text{ }}_{\infty }^{1}\left\{{\left[{\text{Sc}}_{2}{\text{O}}_{6\text{/}1}^{\text{t}}{\text{O}}_{1\text{/}2}^{\text{v}}{\text{O}}_{4\text{/}2}^{\text{e}}\right]}^{11-}\right\}$ chains running along [100], whereas the two [ScO6]9− octahedra in Sc2Te4O11 only share common vertices, generating ∞ 1 { [ Sc 2 O 6 / 1 t O 3 / 2 v ] 9 − } ${\text{ }}_{\infty }^{1}\left\{{\left[{\text{Sc}}_{2}{\text{O}}_{6\text{/}1}^{\text{t}}{\text{O}}_{3\text{/}2}^{\text{v}}\right]}^{9-}\right\}$ double strands along [010]. In both compounds, the three-dimensional framework and the charge balance are accomplished by the discrete ψ1-tetrahedral [TeO3]2− anions with non-bonding lone-pair electrons located at their central Te4+ cations. Moreover, strong secondary Te4+···O2− interactions, which are generally quite common for rare earth metal(III) oxotellurates(IV), occur in both crystal structures, but much more pronounced in Sc2Te4O11, where three quarters of the Te4+ cations reside in the centers of ψ eq 1 ${{\psi}}_{\text{eq}}^{1}$ -trigonal bipyramids [TeO4]4− as compared to Sc2Te3O9, which can well be written as Sc2[TeO3]3.
The ytterbium(III) oxide bromide oxidotellu-rate(IV) Yb3O2Br[TeO3]2 was obtained from a mixture of Yb2O3, YbBr3 and TeO2 in a molar ratio of 2:1:2 along with an excess of KBr as fluxing agent in evacuated fused silica ampoules after 10 days at T = 800 °C and subsequent slow cooling to room temperatures as colorless, plate-shaped single crystals. Its triclinic crystal structure (a = 663.97(5), b = 697.46(5), c = 1080.15(8) pm, α = 105.102(3), β = 90.931(3), γ = 100.034(3)°; Z = 2, space group: P$‾{1}$) displays three crystallographically different Yb3+ cations with coordination numbers of six, seven and eight. Six out of eight distinct oxygen atoms belong to two independent ψ1-tetrahedral [TeO3]2−anions, whereas the other two represent O2− anions in tetrahedral coordination of four Yb3+ cations each, not having any contact to tellurium. Condensed via common vertices and edges, these [OYb4]10+ tetrahedra form cationic layers ${}_{\infty }{}^{2}${[O2Yb3]5+}, which spread out parallel to the (001) plane. Two discrete [TeO3]2− groups and one Br− anion per formula unit take care of their three-dimensional interconnection along [001] and the overall charge balance of Yb3O2Br[TeO3]2. Remarkable interactions between the lone pair of electrons at the Te4+ cations of the ψ1-tetrahedral [TeO3]2− anions and those at the Br− anions are discussed.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.
hi@scite.ai
10624 S. Eastern Ave., Ste. A-614
Henderson, NV 89052, USA
Copyright © 2024 scite LLC. All rights reserved.
Made with 💙 for researchers
Part of the Research Solutions Family.