The synthesis and characterization of the first stable trialkyl(difluoroamino)silane, R3SiNF2, as well as of R3SiNHF and R3SiN(CH3)F in moderate yields are reported. The (difluoroamino)silane has promise as a new synthon for the introduction of the -NF2 group into a variety of electrophilic inorganic and organic substrates. Activation barriers and relative energies were calculated for the unimolecular decompositions of Me3SiCF3 and t-Bu3SiNF2 using density functional theory (B3LYP/6-31G). The calculated activation energies confirm the long-assumed kinetic stability of Me3SiCF3.
Download full-text PDF |
Source |
|---|---|
| http://dx.doi.org/10.1021/jo026201y | DOI Listing |
Publication Analysis
Top Keywords
Similar Publications
SilE-R and SilE-S-DABB Proteins Catalying Enantiospecific Hydrolysis of Organosilyl Ethers.
Angew Chem Int Ed Engl
June 2024
Professur für Molekulare Biotechnologie, Technische Universität Dresden, 01062, Dresden, Germany.
Silyl ethers fulfil a fundamental role in synthetic organic chemistry as protecting groups and their selective cleavage is an important factor in their application. We present here for the first time two enzymes, SilE-R and SilE-S, which are able to hydrolyse silyl ethers. They belong to the stress-response dimeric A/B barrel domain (DABB) family and are able to cleave the Si-O bond with opposite enantiopreference.
View Article and Find Full Text PDFHexagonal Prismatic Siloxanes Functionalized with Organosilyl Groups as Building Blocks of Nanoporous Materials.
Chemistry
March 2024
Department of Applied Chemistry, Faculty of Science and Engineering, Waseda University, 3-4-1 Okubo, Shinjuku-ku, Tokyo, 169-8555, Japan.
Utilization of well-defined siloxane molecules allows for the construction of functional siloxane-based nanoporous materials based on the molecular design. Herein, a novel class of siloxane-based porous materials is synthesized via cross-linking of dimethylsilyl- and dimethylvinylsilyl-functionalized cage siloxanes with double-6-ring (D6R) geometry. Compared with the conventional double-4-ring cage siloxane, this study highlights the characteristics of D6R siloxanes as building blocks, demonstrating their high surface area and chemical stability.
View Article and Find Full Text PDFPlanar three-coordinate iron(II) complexes supported by sterically demanding -Si(SiMe)(SiMeBu) ligands.
Dalton Trans
January 2024
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 4-6-1, Komaba, Meguro-ku, Tokyo 153-8505, Japan.
Sterically demanding organosilyl ligands support the formation of coordinatively unsaturated complexes. In this study, we found that using the ligand -Si(SiMe)(SiMeBu) affords exclusively planar three-coordinate iron bis(silyl) complexes that show good catalytic performance in the hydrosilylation of acetophenone.
View Article and Find Full Text PDFFour- and three-coordinate planar iron(II) complexes supported by bulky organosilyl ligands.
Dalton Trans
October 2023
Department of Applied Chemistry, School of Engineering, The University of Tokyo, 4-6-1, Komaba, Meguro-ku, Tokyo 153-8505, Japan.
The ligand exchange reaction of (THF)Fe[Si(SiMe)] with 2 equivalents of an N-heterocyclic carbene (NHC) led to the formation of a square-planar iron(II) complex with -oriented -Si(SiMe) ligands. Conversely, the introduction of a -coordinate bidentate organosilyl ligand instead of -Si(SiMe) resulted in the formation of a square planar iron(II) complex supported by a -coordinate bidentate organosilyl ligand. A three-coordinate planar iron(II) bis(silyl) complex was also synthesized using a -coordinate bidentate organosilyl ligand and a cyclic (alkyl)(amino)carbene auxiliary ligand.
View Article and Find Full Text PDFSynthesis of Stable Potassium Phosphinophosphides and Reaction with Organosilyl Halides and Chlorophosphanes.
Inorg Chem
May 2023
Institut für Chemie, Universität Rostock Albert-Einstein-Straße 3a, Rostock 18059, Germany.
The synthesis of sterically demanding 2,6-bis(2,4,6-trimethylphenyl)phenyl (Ter)-stabilized and H-substituted diphosphanes TerHP-PR (-) via conversion of the phosphide TerPHK () with secondary chlorophosphanes ClPR (-, where R = Pr, Ph, and Bu, respectively) is described. The diphosphanes - were deprotonated using KH in tetrahydrofuran, selectively yielding the potassium phosphinophosphides K[TerP-PR] (-). These phosphinophosphides are stable in solution as well as in the solid state and can be further functionalized via salt-metathesis reactions.
View Article and Find Full Text PDFWant AI Summaries of new PubMed Abstracts delivered to your In-box?
Enter search terms and have AI summaries delivered each week - change queries or unsubscribe any time!