Vibrational spectra and structure of trimethylindium and trimethylthallium

Kurbakova, A. P.; Bukalov, S. S.; Leites, L. A.; Golubinskaya, L. M.; Bregadze, V. I.

doi:10.1016/s0022-328x(96)06793-9

Cited by 9 publications

(7 citation statements)

References 23 publications

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“…The results of our frequency analyses for EH and EH 3 are given in Tables and along with literature data. The vibrational spectrum of trimethylthallium has been investigated by theoretical and experimental methods in detail in the past and will not be repeated here . Our calculated frequencies are in relatively good agreement with the experimental values for all of the EH and EH 3 molecules, especially for the out of plane (ν 2 ) and in-plane (ν 4 ) bending modes in EH 3 .…”

Section: Resultssupporting

confidence: 62%

Kinetic and Thermodynamic Stability of the Group 13 Trihydrides

et al. 2009

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The kinetic and thermodynamic stabilities of the group 13 hydrides EH(3) (E = B, Al, Ga, In, Tl, E113) are investigated by relativistic density functional and wave function based theories. The unimolecular decomposition of EH(3) --> EH + H(2) becomes energetically more favorable going down the Group 13 elements, with the H(2)-abstraction of InH(3), TlH(3), and (E113)H(3) (E113: element with nuclear charge 113) being exothermic. In accordance with the Hammond-Leffler postulate, the activation barrier for the dissociation process decreases accordingly going down the group 13 elements in the periodic table shifting to an early transition state, with activation energies ranging from 88.4 kcal/mol for BH(3) to 41.3 kcal/mol for TlH(3) and only 21.6 kcal/mol for (E113)H(3) at the scalar relativistic coupled cluster level of theory. For both TlH(3) and (E113)H(3) we investigated spin-orbit effects using Dirac-Hartree-Fock and second-order Møller-Plesset theory to account for electron correlation. For (E113)H, spin-orbit coupling results in a chemically inert closed 7p(1/2)-shell, thus reducing the stability of the higher oxidation state even further. We also investigated the known organothallium compound Tl(CH(3))(3), which is thermodynamically unstable similar to TlH(3), but kinetically very stable with an activation barrier of 57.1 kcal/mol.

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Section: Resultssupporting

confidence: 62%

Kinetic and Thermodynamic Stability of the Group 13 Trihydrides

et al. 2009

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“…Similarly, the X-C stretching modes in (H 3 C) 3 X exhibit small Raman activities, although at higher frequencies: 675, 517, 525, and 478 cm −1 for X = B, Al, Ga, and In, respectively. For comparison, the X-C stretching is experimentally observed for TMB 26 at around 675 cm −1 , for TMA 60 at around 530 cm −1 , for TMG 28 at around 570 cm −1 , and for TMI 29,58 at around 478 cm −1 , which are in good agreement with our theoretical results obtained with the MP2 method.…”

Section: B Reaction Paths For Obtaining the (H 3 C) N X(sih 3 ) 3−n C...supporting

confidence: 90%

“…The most typical features of X(SiH 3 ) 3 appear in the 2260-2300 cm -1 spectral range, while the spectra of (H 3 C) 3 X exhibit their most prominent peaks in the 3050-3180 cm -1 spectral range. For comparison, the X-C stretching is experimentally observed for TMB 26 at around 675 cm -1 , for TMA 60 at around 530 cm -1 , for TMG 28 at around 570 cm -1 , and for TMI 29,58 at around 478 cm -1 , which are in good agreement with our theoretical results obtained with the MP2 method. Our results are in agreement with the experimental data available for the Si-H stretching modes in the HCSiH 3 molecule (2139.1 cm -1 ) 59 and the C-H stretching modes in TMB (2958 and 2875 cm -1 ), 26 TMA (2919 and 2925 cm -1 ), 27 TMG (2990 and 2916 cm -1 ), 28 and TMI (2925 cm -1 ).…”

Section: B Reaction Paths For Obtaining the (H 3 C) N X(sih 3 ) 3-n Csupporting

confidence: 89%

“…26,57,58 Hence, we have calculated the Raman spectra and depolarized light-scattering properties of all (H 3 C) n X(SiH 3 ) 3-n compounds at the MP2 level of theory. 26,57,58 Hence, we have calculated the Raman spectra and depolarized light-scattering properties of all (H 3 C) n X(SiH 3 ) 3-n compounds at the MP2 level of theory.…”

Section: B Reaction Paths For Obtaining the (H 3 C) N X(sih 3 ) 3-n Cmentioning

confidence: 99%

“…For the identification of the structural features of these compounds, it is useful to analyse their vibrational properties, since experimental infrared and Raman spectroscopies may be very suitable for this purpose. 26,57,58 Hence, we have calculated the Raman spectra and depolarized light-scattering properties of all (H 3 C) n X(SiH 3 ) 3−n compounds at the MP2 level of theory.…”

Section: B Reaction Paths For Obtaining the (H 3 C) N X(sih 3 ) 3−n C...mentioning

confidence: 99%

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Feasibility of novel (H₃C)_nX(SiH₃)_3−ncompounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations

et al. 2015

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We employ ab initio calculations to predict the equilibrium structure, stability, reactivity, and Raman scattering properties of sixteen different (H3C)nX(SiH3)3-n compounds (X = B, Al, Ga, In) with n = 0-3. Among this methylsilylmetal family, only the (H3C)3X 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 (H3C)nX(SiH3)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 (H3C)nX(SiH3)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 (H3C)nX(SiH3)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.

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Indium: Organometallic Chemistry

Banger

2005

Encyclopedia of Inorganic Chemistry

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An overview of the chemistry of organoindium compounds containing at least one InC bond over the last ten years is reported in detail. In particular, the synthesis, characterization, properties of homoleptic and heteroleptic organoindium derivatives, organoindium(0), (I), and (II) compounds, and in addition anionic compounds are also reported. Furthermore, the use of organoindium compounds for thin film, nanotechnology, and organic synthesis is discussed.

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Vibrational spectra and structure of trimethylindium and trimethylthallium

Cited by 9 publications

References 23 publications

Kinetic and Thermodynamic Stability of the Group 13 Trihydrides

Kinetic and Thermodynamic Stability of the Group 13 Trihydrides

Feasibility of novel (H₃C)_nX(SiH₃)_3−ncompounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations

Indium: Organometallic Chemistry

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Vibrational spectra and structure of trimethylindium and trimethylthallium

Cited by 9 publications

References 23 publications

Kinetic and Thermodynamic Stability of the Group 13 Trihydrides

Kinetic and Thermodynamic Stability of the Group 13 Trihydrides

Feasibility of novel (H3C)nX(SiH3)3−ncompounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations

Indium: Organometallic Chemistry

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Feasibility of novel (H₃C)_nX(SiH₃)_3−ncompounds (X = B, Al, Ga, In): structure, stability, reactivity, and Raman characterization from ab initio calculations