The gas-phase reactions of SiCl4 and Si2Cl6 with CH3OH and C2H5OH: An investigation by mass spectrometry and matrix-isolation infrared spectroscopy

Goldberg, Nicola; Almond, Matthew J.; Ogden, J. S.; Cannady, J. Pat; Walsh, Robin; Becerra, Rosa

doi:10.1039/b403586k

Cited by 8 publications

(3 citation statements)

References 21 publications

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“…SiCl 4 reacts with both CH 3 OH and C 2 H 5 OH upon mixing the vapours for approximately 3 h and the HCl-elimination products Cl 3 SiOR (R = Me or Et) have been identified by mass spectrometry and matrix isolation. 232 Further products are generated if the reaction mixture is passed through a tube heated to 750 1C. Si 2 Cl 6 reacts with CH 3 OH and C 2 H 5 OH via a different mechanism in which the Si-Si bond is cleaved to yield Cl 3 SiOR and HCl.…”

Section: Inorganic Compoundsmentioning

confidence: 99%

Chemistry in low-temperature matrices

Almond

Goldberg

2007

Annu. Rep. Prog. Chem., Sect. C: Phys. Chem.

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the Progress of Chemistry, Section C. The report is divided into sections: weak adducts and conformational isomers; reactions of atoms; high-temperature molecules; photochemistry; biological molecules; astrochemistry. The last two sections reflect the fact that matrix isolation now extends into areas outside the traditional mainstream disciplines of chemistry. There are a number of areas where substantial progress has been made during the period of this report. First, the routine use of laser-ablation to generate atoms and to initiate atomic reactions in matrices has increased the scope of matrix isolation to synthesise many new molecular species in inorganic chemistry. Laser-ablation allows ground state atoms to be more easily studied than is the case when atoms are produced by thermal methods. Moreover, this procedure allows atoms to be generated from materials where thermal production is difficult. Secondly, the manufacture of more efficient closed-cycle helium refrigerators allows hydrogen matrices to be deposited readily. A significant body of work therefore has focussed upon metal hydrides, dihydrogen complexes and other hydrogen species in matrices. Underpinning all of this experimental work are theoretical calculations, without which the correct identification of most matrix isolation molecules would remain dangerously ambiguous. Infrared spectroscopy remains-as it has for the past 50 years-the workhorse of matrix isolation studies. It does seem that this situation will not change-it is impossible to conceive of another spectroscopic method that combines the necessary sensitivity to study molecules at very low dilution with the structural information required to make a reasonably certain identification.

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Section: Inorganic Compoundsmentioning

confidence: 99%

Chemistry in low-temperature matrices

Almond

Goldberg

2007

Annu. Rep. Prog. Chem., Sect. C: Phys. Chem.

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“…Generally, noble gases such as argon are chosen to form a hosting matrix because of their inert nature as well as broad optical transparency. Using this matrix isolation technique, short-lived, highly reactive species can be trapped and analyzed by spectroscopic means. − This method was later adopted to probe the activities of metals or metal oxides toward a reactive matrix. − For instance, (MoO 3 ) 3 or (WO 3 ) 3 clusters were deposited into a reactive matrix of ethanol to study the clusters’ dehydration and oxidation properties toward ethanol . A graphene thin film over Pt(111) was chosen as an inert substrate not only for its unreactivity toward alcohols, but also to minimize the substrate’s effects on the acidic and redox properties of those metal oxide clusters .…”

Section: Introductionmentioning

confidence: 99%

Combined TPD and XPS Study of Ligation and Decomposition of 1,6-Hexanedithiol on Size-Selected Copper Clusters Supported on HOPG

et al. 2018

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Ligation and decomposition of 1,6-hexanedithiol on copper clusters have been studied by means of temperature-programmed desorption (TPD) and X-ray photoelectron spectroscopy (XPS). Copper cluster anions were first made via magnetron sputtering, then size selected and soft landed into a frozen matrix of 1,6-hexandithiol on highly ordered pyrolytic graphite (HOPG) maintained at 100 K. After warming up to 298 K, a combination of TPD and XPS were performed to characterize the newly deposited sample. TPD data shed light upon the adsorption and decomposition pathways of 1,6-hexanedithiol molecules on copper clusters. Based on the TPD data, two different binding motifs are proposed: the dangling motif is with one sulfur atom binding to a copper cluster, and the bidentate motif is with both sulfur atoms binding to a copper cluster. Different decomposition products were observed for each binding motif. A series of hydrogen atom titration experiments were designed to provide further evidence for the proposed decomposition mechanism. XPS measurements at varied temperatures agree well with the TPD profile by confirming the formation of dithiol ligated copper clusters through Cu–S bond formation, and the decomposition of them via C–S bond scission. How well the dithiol ligand can protect the copper clusters from being oxidized is discussed, and the ligand number per cluster is estimated.

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“…Correction for the ion gauge readings to obtain the absolute pressure of SiCl 4 leads to a rate constant of (2.3 AE 0.7) Â 10 À10 cm 3 molecule À1 s À1 at a cell temperature of 333 AE 5 K. This value is of the order of 10% of the calculated ion-neutral collision rate constant. The fact that no equivalent reaction to (1) has been previously observed in the neutral chemistry of SiCl 4 and Si 2 Cl 6 [27][28][29][30][31] prompted us to investigate more thoroughly the mechanism of reaction (1). This is of considerable interest because of the important role that chlorosiloxane species play in the functionalization of silica particles.…”

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confidence: 99%