Feasibility of novel (H3C)nX(SiH3)3−n compounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculationsElectronic supplementary information (ESI) available: Details of the lowest frequencies, molecular dipole moments, optimized structures, frontier orbitals, Bader analysis, and reaction paths for all (CH3)nX(SiH3)3−n compounds. See DOI: 10.1039/c4dt03406f

We employ ab initio calculations to predict the equilibrium structure, stability, reactivity, and Raman scattering properties of sixteen different (H 3 C) n X(SiH 3 ) 3− n compounds (X = B, Al, Ga, In) with n = 0-3. Among this methylsilylmetal family, only the (H 3 C) 3 X members, i.e. , trimethylboron (TMB), trimethylaluminum (TMA), trimethylgallium (TMG), and trimethylindium (TMI), are currently well-studied. The remaining twelve compounds proposed here open up a two-dimensional array of new possibilities for precursors in various deposition processes, and evoke potential applications in the chemical synthesis of other compounds. We infer that within the (H 3 C) n X(SiH 3 ) 3− n family, the compounds with fewer silyl groups (and consequently with more methyl groups) are less reactive and more stable. This trend is verified from the calculated cohesive energy, Gibbs free energy of formation, bond strength, and global chemical indices. Furthermore, we propose sequential reaction routes for the synthesis of (H 3 C) n X(SiH 3 ) 3− n by substitution of methyl by silyl groups, where the silicon source is the silane gas. The corresponding reaction barriers for these chemical transformations lie in the usual energy range typical for MOCVD processes. We also report the Raman spectra and light scattering properties of the newly proposed (H 3 C) n X(SiH 3 ) 3− n compounds, in comparison with available data of known members of this family. Thus, our computational experiment provides useful information for a systematic understanding of the stability/reactivity and for the identification of these compounds. Stability of the (H 3 C) n X(SiH 3 ) 3− n compounds.