DMF-activated chlorosilane chemistry: Molybdenum-catalyzed reactions of R3SiH, DMF and R′3SiCl to initially form R′3SiOSiR′3 and R3SiCl

Gonzalez, Paulina E.; Sharma, Hemant; Pannell, Keith H.

doi:10.1016/j.ica.2017.06.010

Cited by 4 publications

(3 citation statements)

References 28 publications

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“…1 (4-Bromophenoxy)trimethylsilane [38] (3q) was obtained as colorless oil in 92 % yield. 1 1,1,1-Triethyl-3,3,3-trimethyldisiloxane [82] (5aa) was obtained as colorless oil in 79 % yield. 1 H NMR (400 MHz, CDCl 3 ) δ (ppm) = 0.96 (t, J = 7.9 Hz, 9H), 0.53 (q, J = 7.9 Hz, 6H), 0.10 (s, 9H).…”

Section: Gram-scale Synthesis Of 2-(2-propenyloxy)ethoxytrimethylsilamentioning

confidence: 99%

Silylation of Alcohols, Phenols, and Silanols with Alkynylsilanes – an Efficient Route to Silyl Ethers and Unsymmetrical Siloxanes

2020

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The formation of several silyl ethers (alkoxysilanes, R3Si‐OR') and unsymmetrical siloxanes (R3Si‐O‐SiR'3) can be catalyzed by the commercially available potassium bis(trimethylsilyl)amide (KHMDS). The reaction proceeds via direct dealkynative coupling between various alcohols or silanols and alkynylsilanes, with a simultaneous formation of gaseous acetylene as the sole by‐product. The dehydrogenative and dealkenative coupling of alcohols or silanols are well‐investigated, whilst the utilization of alkynylsilanes as silylating agents has never been comprehensively studied in this context. Overall, the presented system allows the synthesis of various attractive organosilicon compounds under mild conditions, making this approach an atom‐efficient, environmentally benign, and sustainable alternative to existing synthetic solutions.

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Section: Gram-scale Synthesis Of 2-(2-propenyloxy)ethoxytrimethylsilamentioning

confidence: 99%

Silylation of Alcohols, Phenols, and Silanols with Alkynylsilanes – an Efficient Route to Silyl Ethers and Unsymmetrical Siloxanes

2020

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“…Formation of chloroimminium siloxyl ion pairs (I) might be initiated by the coordination of DMF O atoms to surface Si, supported by the high affinity of Si and O atoms. , Further reaction of I to yield siloxymethylamine Me 2 NCH 2 OSiNP (structure II in Scheme ) may take place in the presence of SiNPs containing surface Si–H groups. Also, decomposition of surface chloroimminium siloxyl ion pairs (I) to compound III and oxidized SiNPs may explain the observed partial oxidation of the SiNP surface during nanoparticle synthesis (vide supra).…”

Section: Resultsmentioning

confidence: 99%

Incorporation of N and O into the Shell of Silicon Nanoparticles Offers Tunable Photoluminescence for Imaging Uses

Romero¹,

Dell’Arciprete

Rodríguez

et al. 2022

ACS Appl. Nano Mater.

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Silicon nanoparticles (SiNPs) show tunable photoluminescence (PL), water-dispersibility, high photostability, and low cytotoxicity, thus constituting promising candidates for bioimaging applications. Because SiNP PL depends finely on particles’ crystallinity and surface composition, specific tuning of PL properties has remained elusive. Herein, using steady and time-resolved PL studies, absorbance spectroscopy, and electrochemical techniques, we have deeply analyzed the origin of the PL of SiNPs obtained from a wet chemical synthesis procedure based on the oxidation of Zintl salts in dimethyl formamide (DMF). Obtained SiNPs, surface-functionalized with propylamine terminal groups, were amorphous and 2.8–3.7 nm in size. The photophysical evidence, together with XPS and FTIR spectroscopy, supported a core–shell structure of the nanoparticles consisting of a silicon core surrounded by a 0.7–1.25 nm-thick oxidized silicon shell containing low concentrations of trapped iminium siloxyl ions or related compounds. The introduction of N-functionalities in the nanoparticle shell was assigned to the reaction of Si–Cl and Si–H bonds formed during synthesis, with DMF. The use of increasing amounts of NH4Cl in the synthesis procedure led to more oxidized shell structures of SiNPs. It is suggested that the presence of an oxidized silicon shell containing trapped iminium siloxyl ions provided a high density of localized states capable of quenching the core-state emission and of being themselves populated by absorption of visible light. Moreover, it was experimentally confirmed that emission preferentially takes place from localized states introduced by O-functionalities with a high quantum efficiency (ηPL‑trap ≅ 1). As fluorophores, the obtained SiNPs display tunable PL emission and an important red-edge shift, allowing the selection of the PL by changing the excitation wavelength without modification of its chemical composition and size, thus meeting the needs of various types of biosensing methods.

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“…13,14 It can be used as a multipurpose reagent that delivers its own H, C, N and O atoms for the synthesis of a variety of compounds under different experimental conditions. 15–17 The significant advances inspired us to explore more highly efficient transformations based on the Ag–H species using DMF as an oxygen supplier. To the best of our knowledge, DMF has seldom been used as a reagent to achieve disiloxanes in a silver( i ) catalytic system.…”

Section: Introductionmentioning

confidence: 99%

Silver(i)-catalyzed oxidative coupling of hydrosilanes with DMF to symmetrical and unsymmetrical disiloxanes

Dong

et al. 2022

New J. Chem.

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DMF-activated chlorosilane chemistry: Molybdenum-catalyzed reactions of R3SiH, DMF and R′3SiCl to initially form R′3SiOSiR′3 and R3SiCl

Cited by 4 publications

References 28 publications

Silylation of Alcohols, Phenols, and Silanols with Alkynylsilanes – an Efficient Route to Silyl Ethers and Unsymmetrical Siloxanes

Silylation of Alcohols, Phenols, and Silanols with Alkynylsilanes – an Efficient Route to Silyl Ethers and Unsymmetrical Siloxanes

Incorporation of N and O into the Shell of Silicon Nanoparticles Offers Tunable Photoluminescence for Imaging Uses

Silver(i)-catalyzed oxidative coupling of hydrosilanes with DMF to symmetrical and unsymmetrical disiloxanes

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