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The Synthesis of [Sn10(Si(SiMe3)3)4]2- Using a Metastable Sn(I) Halide Solution Synthesized via a Co-condensation Technique
Published on: November 28, 2016
Structural and thermodynamic properties of group 13 imidometallanes and their heavier analogues
Alexey Y Timoshkin1, Henry F Schaefer
1Department of Chemistry, St Petersburg State University, University Pr. 26, Old Peterhof, 198504, Russia. alex-tim@AT11692.spb.edu
Abstract:
Systematic theoretical studies of the [XMYH](n) inorganic rings and clusters (M = Al, Ga, In; Y = N, P, As; X = H, F, Cl, Br, I; n = 1-6) have been carried out using hybrid Hartree-Fock density functional theory. A consistent set of the structural and thermodynamic properties has been obtained. The stability of the MY bond decreases in the order Al > Ga >or= In; N >> P > As. Terminal groups X have a minor influence on the subsequent elimination enthalpies of the clusters. In the case of X = H, hydrogen elimination makes formation of the [HMYH](6) oligomers from MH(3) and YH(3) thermodynamically favorable; while in the case of halide substituents, formation of [XMYH](6) is thermodynamically unfavorable, except for the system with the strongest MY bond (AlN). Substitution of the acidic hydrogen by X is favorable energetically for all [HMYH](6) clusters, but is complicated by the processes of cluster destruction to form the [X(2)MYH(2)](2) dimers. The high stability of the [HMNH](6) clusters makes them attractive single-source precursors for the production of 13-15 composites.
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