Bond dissociation energies of FeSi, RuSi, OsSi, CoSi, RhSi, IrSi, NiSi, and PtSi

Sevy, Andrew; Tieu, Erick; Morse, Michael D.

doi:10.1063/1.5050934

Cited by 27 publications

(18 citation statements)

References 81 publications

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“…They do not undergo Pt−Si bond cleavage under heating (through cyclometalation processes) nor upon pressurizing with H 2 (4 atm), their solutions remaining unaltered. This is consistent with the known strength of the Pt−Si bond …”

Section: Resultssupporting

confidence: 90%

“…This is consistentw ith the known strength of the PtÀSi bond. [15] Yellow crystals suitable for X-ray diffraction studies were grown for complex 4.2 a (Figure 3). The structure of the cation features the expected trans arrangement of the two NHC ligands,w itht he third coordination site occupiedb yt he silyl ligand.T he two NHC ligands are tiltedw ith respect to the coordination plane aboutt he platinum center,b ut at considerably different angles of 76.98 and 40.38,tom inimize steric repulsion between the mesityl rings.…”

Section: Reactionsofp Rimary Silanes With Platinumh Ydride Complexes mentioning

confidence: 99%

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σ‐Silane Platinum(II) Complexes as Intermediates in C−Si Bond‐Coupling Processes

Ríos

Fouilloux

Dı́ez

et al. 2019

Chemistry A European J

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Platinumc omplexes [Pt(NHC')(NHC)][BAr F ]( in which NHC' denotes ac yclometalated N-heterocyclic carbene ligand, NHC) react with primary silanes RSiH 3 to afford the cyclometalated platinum(II) silyl complexes [Pt(NHC-SiHR')(NHC)][BAr F ]t hrough ap rocess that involves the formation of CÀSi and PtÀSi bonds with concomitante xtrusion of H 2 .L ow-temperature NMR studies indicatet hat the process proceeds through initial formation of the s-SiH complexes [Pt(NHC')(NHC)(HSiH 2 R)][BAr F ], which are stable at temperatures below À10 8C. At highert emperatures, activation of one SiÀHb ond followed by aC ÀSi coupling reaction generates an agostic SiH platinum hydride derivative [Pt(H)(NHC'-SiH 2 R)(NHC)][BAr F ], whichu ndergoes as econd SiÀHb ond activation to afford the final products. Computationalm odeling of the reaction mechanism indicates that the stereochemistry of the silyl/hydride ligands after the first SiÀHb ond cleavage dictates the nature of the products, favoringthe formation of aC ÀSi bond over aC ÀHb ond, in contrastt op revious results obtained for tertiary silanes. Furthermore, the processi nvolves a trans-to-cis isomerization of the NHC ligand beforet he second SiÀHbond cleavage.

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Section: Resultssupporting

confidence: 90%

Section: Reactionsofp Rimary Silanes With Platinumh Ydride Complexes mentioning

confidence: 99%

σ‐Silane Platinum(II) Complexes as Intermediates in C−Si Bond‐Coupling Processes

Ríos

Fouilloux

Dı́ez

et al. 2019

Chemistry A European J

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“…(Goos, Burcat, & Ruscic). g Experimental value from Sevy et al (2018). h Experimental value from Stearns & Kohl (1974).…”

Section: Appendix A10: Aluminummentioning

confidence: 99%

Chemical equilibrium in AGB atmospheres: successes, failures, and prospects for small molecules, clusters, and condensates

Agúndez

Martínez

Andrés

et al. 2020

A&A

107

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Chemical equilibrium has proven extremely useful for predicting the chemical composition of AGB atmospheres. Here we use a recently developed code and an updated thermochemical database that includes gaseous and condensed species involving 34 elements to compute the chemical equilibrium composition of AGB atmospheres of M-, S-, and C-type stars. We include for the first time Ti x C y clusters, with x = 1-4 and y = 1-4, and selected larger clusters ranging up to Ti 13 C 22 , for which thermochemical data are obtained from quantum-chemical calculations. Our main aims are to systematically survey the main reservoirs of each element in AGB atmospheres, review the successes and failures of chemical equilibrium by comparing it with the latest observational data, identify potentially detectable molecules that have not yet been observed, and diagnose the most likely gas-phase precursors of dust and determine which clusters might act as building blocks of dust grains. We find that in general, chemical equilibrium reproduces the observed abundances of parent molecules in circumstellar envelopes of AGB stars well. There are, however, severe discrepancies of several orders of magnitude for some parent molecules that are observed to be anomalously overabundant with respect to the predictions of chemical equilibrium. These are HCN, CS, NH 3 , and SO 2 in M-type stars, H 2 O and NH 3 in S-type stars, and the hydrides H 2 O, NH 3 , SiH 4 , and PH 3 in C-type stars. Several molecules have not yet been observed in AGB atmospheres but are predicted with nonnegligible abundances and are good candidates for detection with observatories such as ALMA. The most interesting ones are SiC 5 , SiNH, SiCl, PS, HBO, and the metal-containing molecules MgS, CaS, CaOH, CaCl, CaF, ScO, ZrO, VO, FeS, CoH, and NiS. In agreement with previous studies, the first condensates predicted to appear in C-rich atmospheres are found to be carbon, TiC, and SiC, while Al 2 O 3 is the first major condensate expected in O-rich outflows. According to our chemical equilibrium calculations, the gas-phase precursors of carbon dust are probably acetylene, atomic carbon, and/or C 3 , while for silicon carbide dust, the most likely precursors are the molecules SiC 2 and Si 2 C. In the case of titanium carbide dust, atomic Ti is the major reservoir of this element in the inner regions of AGB atmospheres, and therefore it is probably the main supplier of titanium during the formation of TiC dust. However, chemical equilibrium predicts that large titanium-carbon clusters such as Ti 8 C 12 and Ti 13 C 22 become the major reservoirs of titanium at the expense of atomic Ti in the region where condensation of TiC is expected to occur. This suggests that the assembly of large Ti x C y clusters might be related to the formation of the first condensation nuclei of TiC. In the case of Al 2 O 3 dust, chemical equilibrium indicates that atomic Al and the carriers of Al-O bonds AlOH, AlO, and Al 2 O are the most likely gas-phase precursors.

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“…It has been successfully used to synthesize topological MSi materials, which have soared lately in the condensed matter physics field. [ 24–29 ] We were not only able to fabricate the previously reported RuSi more readily but also successfully synthesized the TiSi electrocatalyst for the first time. Moreover, we extensively explored 8 MSi as HER catalysis.…”

Section: Introductionmentioning

confidence: 98%

Discovery and Facile Synthesis of a New Silicon Based Family as Efficient Hydrogen Evolution Reaction Catalysts: A Computational and Experimental Investigation of Metal Monosilicides

Wang

Zhang

et al. 2021

Small

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A new family of transition‐metal monosilicides (MSi, M = Ti, Mn, Fe, Ru, Ni, Pd, Co, and Rh) electrocatalysts with superior electrocatalytic performance of hydrogen evolution is reported, based on the computational and experimental results. It is proposed that these MSi can be synthesized within several minutes by adopting the arc‐melting method. The previously reported RuSi is not only fabricated more readily but eventually explored 8 MSi that can be good hydrogen evolution reaction catalysts. Silicides then can be another promising electrocatalysts family as carbides, wherein carbon has the same electronic configuration as silicon. All explored silicides electrodes exhibited low overpotentials (34–54 mV at 10 mA cm−2) with Tafel slopes from 23.6 to 32.3 mV dec−1, which are comparable to that of the commercial 20 wt% Pt/C (37 mV, 26.1 mV dec−1). First‐principles calculations demonstrated that the superior performance can be attributed to the high catalytic reactivity per site that can even function at high hydrogen coverages (≈100%) on multiple low surface energy facets. The work sheds light on a new class of electrocatalysts for hydrogen evolution, with earth‐abundant and inexpensive silicon‐based compounds.

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Bond dissociation energies of FeSi, RuSi, OsSi, CoSi, RhSi, IrSi, NiSi, and PtSi

Cited by 27 publications

References 81 publications

σ‐Silane Platinum(II) Complexes as Intermediates in C−Si Bond‐Coupling Processes

σ‐Silane Platinum(II) Complexes as Intermediates in C−Si Bond‐Coupling Processes

Chemical equilibrium in AGB atmospheres: successes, failures, and prospects for small molecules, clusters, and condensates

Discovery and Facile Synthesis of a New Silicon Based Family as Efficient Hydrogen Evolution Reaction Catalysts: A Computational and Experimental Investigation of Metal Monosilicides

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