The hydrolysis of (OSi)-chelate [N-(acetamido)methyl]dimethylchlorosilanes. DFT and MP2 study, QTAIM and NBO analysis

Chípanina, N. N.; Lazareva, N. F.; Oznobikhina, Larisa P.; Lazarev, I. M.; Shainyan, B. А.

doi:10.1016/j.comptc.2015.08.008

Cited by 5 publications

(1 citation statement)

References 53 publications

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“…A backside attack at the silicon in dichlorosilane 7 and monochlorosilanol 8 is blocked by the backbone, making a consideration of the mechanism not necessary. A mechanism with a pentacoordination at the silicon is assumed for the hydrolyses of BIFOXSiCl 2 ( 7 ) to BIFOXSiCl(OH) ( 8 ) as intermediate and BIFOXSI(OH) 2 ( 9 ) as product [65–67]. Two pathways (front attack mechanism (front) or side attack mechanism (side)) for the approaching water molecule are considered (Scheme 5).…”

Section: Resultsmentioning

confidence: 99%

Silanediol versus chlorosilanol: hydrolyses and hydrogen-bonding catalyses with fenchole-based silanes

Fox

Neudörfl

Goldfuß

2019

Beilstein J. Org. Chem.

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Biphenyl-2,2’-bisfenchyloxydichlorosilane (7, BIFOXSiCl2) is synthesized and employed as precursor for the new silanols biphenyl-2,2’-bisfenchyloxychlorosilanol (8, BIFOXSiCl(OH)) and biphenyl-2,2’-bisfenchyloxysilanediol (9, BIFOXSi(OH)2). BIFOXSiCl2 (7) shows a remarkable stability against hydrolysis, yielding silanediol 9 under enforced conditions. A kinetic study for the hydrolysis of dichlorosilane 7 shows a 263 times slower reaction compared to reference bis-(2,4,6-tri-tert-butylphenoxy)dichlorosilane (14), known for its low hydrolytic reactivity. Computational analyses explain the slow hydrolyses of BIFOXSiCl2 (7) to BIFOXSiCl(OH) (8, E a = 32.6 kcal mol−1) and BIFOXSiCl(OH) (8) to BIFOXSi(OH)2 (9, E a = 31.4 kcal mol−1) with high activation barriers, enforced by endo fenchone units. Crystal structure analyses of silanediol 9 with acetone show shorter hydrogen bonds between the Si–OH groups and the oxygen of the bound acetone (OH···O 1.88(3)–2.05(2) Å) than with chlorosilanol 8 (OH···2.16(0) Å). Due to its two hydroxy units, the silanediol 9 shows higher catalytic activity as hydrogen bond donor than chlorosilanol 8, e.g., C–C coupling N-acyl Mannich reaction of silyl ketene acetals 11 with N-acylisoquinolinium ions (up to 85% yield and 12% ee), reaction of 1-chloroisochroman (18) and silyl ketene acetals 11 (up to 85% yield and 5% ee), reaction of chromen-4-one (20) and silyl ketene acetals 11 (up to 98% yield and 4% ee).

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Section: Resultsmentioning

confidence: 99%

Silanediol versus chlorosilanol: hydrolyses and hydrogen-bonding catalyses with fenchole-based silanes

Fox

Neudörfl

Goldfuß

2019

Beilstein J. Org. Chem.

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Stabilization of halide perovskites with silicon compounds for optoelectronic, catalytic, and bioimaging applications

Jana,

Cho,

Meena

et al. 2024

InfoMat

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Silicon belongs to group 14 elements along with carbon, germanium, tin, and lead in the periodic table. Similar to carbon, silicon is capable of forming a wide range of stable compounds, including silicon hydrides, organosilicons, silicic acids, silicon oxides, and silicone polymers. These materials have been used extensively in optoelectronic devices, sensing, catalysis, and biomedical applications. In recent years, silicon compounds have also been shown to be suitable for stabilizing delicate halide perovskite structures. These composite materials are now receiving a lot of interest for their potential use in various real‐world applications. Despite exhibiting outstanding performance in various optoelectronic devices, halide perovskites are susceptible to breakdown in the presence of moisture, oxygen, heat, and UV light. Silicon compounds are thought to be excellent materials for improving both halide perovskite stability and the performance of perovskite‐based optoelectronic devices. In this work, a wide range of silicon compounds that have been used in halide perovskite research and their applications in various fields are discussed. The interfacial stability, structure–property correlations, and various application aspects of perovskite and silicon compounds are also analyzed at the molecular level. This study also explores the developments, difficulties, and potential future directions associated with the synthesis and application of perovskite‐silicon compounds.image

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Substituent effect on the hydrolysis of chlorosilanes: quantum chemical and QSPR study

Szabó

Nyulászi

2016

Struct Chem

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The hydrolysis of (OSi)-chelate [N-(acetamido)methyl]dimethylchlorosilanes. DFT and MP2 study, QTAIM and NBO analysis

Cited by 5 publications

References 53 publications

Silanediol versus chlorosilanol: hydrolyses and hydrogen-bonding catalyses with fenchole-based silanes

Silanediol versus chlorosilanol: hydrolyses and hydrogen-bonding catalyses with fenchole-based silanes

Stabilization of halide perovskites with silicon compounds for optoelectronic, catalytic, and bioimaging applications

Substituent effect on the hydrolysis of chlorosilanes: quantum chemical and QSPR study

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