Cationic Carboxylato Complexes of Dirhodium(II) with Oxo Thioethers: Catalysts for Silane Alcoholysis under Homogeneous and Liquid-Liquid Biphasic Conditions

2007 ◽  
Vol 349 (16) ◽  
pp. 2485-2492 ◽  
Author(s):  
Andrea Biffis ◽  
Marino Basato ◽  
Marianna Brichese ◽  
Luca Ronconi ◽  
Cristina Tubaro ◽  
...  
Keyword(s):  
Silane Alcoholysis

scholarly journals Catalytic Asymmetric Silane Alcoholysis: Practical Access to Chiral Silanes.

ChemInform ◽  
2003 ◽  
Vol 34 (25) ◽  
Author(s):  
Darby R. Schmidt ◽  
Steven J. O'Malley ◽  
James L. Leighton
Keyword(s):  
Catalytic Asymmetric ◽  
Silane Alcoholysis

Regioselective Silylation of Sugars through Palladium Nanoparticle-Catalyzed Silane Alcoholysis

2002 ◽  
Vol 124 (35) ◽  
pp. 10508-10518 ◽  
Author(s):  
Mee-Kyung Chung ◽  
Galina Orlova ◽  
John D. Goddard ◽  
Marcel Schlaf ◽  
Robert Harris ◽  
...  
Keyword(s):  
Palladium Nanoparticle ◽  
Regioselective Silylation ◽  
Silane Alcoholysis

scholarly journals Mechanistic Study of Silane Alcoholysis Reactions with Self-Assembled Monolayer-Functionalized Gold Nanoparticle Catalysts

Catalysts ◽  
2020 ◽  
Vol 10 (8) ◽  
pp. 908
Author(s):  
Katsuhiro Isozaki ◽  
Tomoya Taguchi ◽  
Kosuke Ishibashi ◽  
Takafumi Shimoaka ◽  
Wataru Kurashige ◽  
...  
Keyword(s):  
Catalytic Activity ◽  
Metallic Nanoparticles ◽  
Molecular Structures ◽  
Critical Parameters ◽  
Mechanistic Study ◽  
Self Assembled Monolayer ◽  
Mechanistic Investigation ◽  
Self Assembled ◽  
20 Nm ◽  
Silane Alcoholysis

The self-assembled monolayer (SAM)-modified metallic nanoparticles (MNPs) often exhibit improved chemoselectivity in various catalytic reactions by controlling the reactants’ orientations adsorbed in the SAM; however, there have been a few examples showing that the reaction rate, i.e., catalytic activity, is enhanced by the SAM-modification of MNP catalysts. The critical parameters that affect the catalytic activity, such as the supports, nanoparticle size, and molecular structures of the SAM components, remain uninvestigated in these sporadic literature precedents. Here, we report the mechanistic investigation on the effects of those parameters on the catalytic activity of alkanethiolate SAM-functionalized gold nanoparticles (AuNPs) toward silane alcoholysis reactions. The evaluation of the catalytic reaction over two-dimensionally arrayed dodecanethiolate SAM-functionalized AuNPs with different supports revealed the electronic interactions between AuNPs and the supports contributing to the rate enhancement. Additionally, an unprecedented size effect appeared—the AuNP with a 20 nm radius showed higher catalytic activity than those at 10 and 40 nm. Infrared reflection–absorption spectroscopy revealed that the conformational change of alkyl chains of the SAM affects the entrapment of reactants and products inside the SAM, and therefore brings about the acceleration effect. These findings provide a guideline for further applying the SAM-functionalization technique to stereoselective organic transformations with designer MNP catalysts.

Nature of the active silane alcoholysis catalyst in the RuwClx(CO)y(PMe3)z (w, x, y, z = 1 or 2) system; Ru2(µ-Cl)2Cl2(CO)4(PMe3)2 as a new catalyst for silane alcoholysis in a polar solvent

2001 ◽  
Vol 79 (5-6) ◽  
pp. 949-957 ◽  
Author(s):  
Mee-Kyung Chung ◽  
George Ferguson ◽  
Valerie Robertson ◽  
Marcel Schlaf
Keyword(s):  
Dynamic Behaviour ◽  
Polar Solvent ◽  
Variable Temperature ◽  
Model System ◽  
Dimeric Complex ◽  
X Ray ◽  
H Nmr ◽  
Nonpolar Solvents ◽  
Solid State Structures ◽  
Silane Alcoholysis

The dimeric complex Ru2(µ-Cl)2Cl2(CO)4(PMe3)2 (1) forms an active silane alcoholysis complex in the polar solvent N,N-dimethylamino-acetamide (DMA). The dynamic behaviour of 1 in DMF-d7 solution has been investigated by variable temperature (VT) 1H NMR. The solid state structures of 1 and cis,cis,trans-RuCl2(CO)2(PMe3)2 (3) have been determined by single crystal X-ray diffractometry. Using ethylene glycol - triethylsilane as a model system, the catalytic activity of 1 in DMA is compared to that of a series of known silane alcoholysis catalysts, including RhCl(PPh3)3, PdX2 (X = Cl-, OAc-), and cis,cis,trans-[IrH2S2L2]SbF6 (L = PPh3, S = THF). Complex 3 is not an active silane alcoholysis catalyst in this solvent, but is active in nonpolar solvents. Its structure and spectroscopic signature is, however, different from that of a previously reported catalyst of the same composition.Key words: silane alcoholysis, polar solvent, ruthenium catalyst.

First examples of gold nanoparticles catalyzed silane alcoholysis and silylative pinacol coupling of carbonyl compounds

2008 ◽  
Vol 49 (20) ◽  
pp. 3221-3224 ◽  
Author(s):  
Patrizio Raffa ◽  
Claudio Evangelisti ◽  
Giovanni Vitulli ◽  
Piero Salvadori
Keyword(s):  
Gold Nanoparticles ◽  
Carbonyl Compounds ◽  
Pinacol Coupling ◽  
Silane Alcoholysis

ChemInform Abstract: Cationic Carboxylato Complexes of Dirhodium(II) with Oxo Thioethers: Catalysts for Silane Alcoholysis under Homogeneous and Liquid-Liquid Biphasic Conditions.

ChemInform ◽  
2008 ◽  
Vol 39 (15) ◽  
Author(s):  
Andrea Biffis ◽  
Marino Basato ◽  
Marianna Brichese ◽  
Luca Ronconi ◽  
Cristina Tubaro ◽  
...  
Keyword(s):  
Silane Alcoholysis
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