Rhodium(III)‐NSi Catalyzed Styrene Hydrosilylation: Evidence of the Hemilabile Character of NSi‐type Ligands

Chemistry - A European Journal, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 21, 2025

The 18e saturated rhodium(III) species [Rh(H)(X)(κ2-NSitBu2)(bipyMe2)] (NSitBu2={4-methylpyridine-2-yloxy}ditertbutylsilyl; bipyMe2=4,4'-dimethylbipyridine) (X=Cl, 1; OTf, 2) have been prepared and characterized by NMR spectroscopy in the case of 2 it has possible to determine its solid-state structure X-ray diffraction. Complex 1 proven be an effective catalyst precursor for reaction styrene derivatives with hydrosilanes CD2Cl2. However, under catalytic conditions complex decomposes. performance 1-catalyzed strongly depends on nature silane, best was achieved using HSiMe2Ph. Theoretical 1H studies indicate that hemilabile NSi ligand is key understanding activity compound 1.

Language: Английский

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Catalytic Asymmetric Dehydrogenative Si–H/X–H Coupling toward Si-Stereogenic Silanes

Accounts of Chemical Research, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 22, 2025

ConspectusChiral organosilicon compounds bearing a Si-stereogenic center have attracted increasing attention in various scientific communities and appear to be topic of high current relevance modern organic chemistry, given their versatile utility as chiral building blocks, reagents, auxiliaries, catalysts. Historically, access these non-natural silanes mainly relies on resolution, whereas asymmetric synthetic methods dramatically lagged compared carbon counterparts. Over the past two decades, transition-metal-catalyzed desymmetrization prochiral organosilanes has emerged an effective tool for synthesis enantioenriched silanes. Despite progress, catalytic reactions usually suffer from limited substrate scope, poor functional-group tolerance, low enantioselectivity. The growing demand with structural diversity continued drive development new practical assembly molecules.Five years ago, our research group embarked project aimed at developing general approach that can unlock functionalized efficiency. This Account describes laboratory's endeavor exploration dehydrogenative Si–H/X–H coupling toward features (1) readily accessible dihydrosilane starting materials; (2) diverse X–H (X═C, N, O, etc.) partners; (3) platform transformable monohydrosilane products; (4) efficiency atomic economy.At initial stage research, biaryl was selected model conduct enantioselective intramolecular C–H/Si–H reaction. Rh/Josiphos system found early this process, while final enantiocontrol elusive. Mechanistic studies indicated rhodium silyl dihydride complex is resting state cycle, which may undergo racemization center. Enlightened by mechanistic investigations, strategies, tandem alkene hydrosilylation strategy bulky alkene-assisted strategy, were adopted avoid racemization, delivering corresponding 9-silafluorenes excellent yields enantioselectivities. Further C(sp2)–H or C(sp3)–H silylation gave series five-, six- seven-membered heterocycles Next, we extended reaction intermolecular version, realizing Si–H/C–H, Si–H/O–H, Si–H/N–H variety acyclic monohydrosilanes, ethers, siloxanes, silanols, silazanes. We also presented endeavors apply resulting compounds, including further derivatization, polymerization, chiroptical property successfully introduced Si-stereocenters into bioactive molecules, polymers, materials. Lastly, based understanding metal species, developed type ligand applied enable atroposelective anticipate methodology, insights, studies, will not only inspire chemistry but contribute creation novel molecules medicinal materials science.

Language: Английский

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X-Type Silyl Ligands Mediated C—H Functionalization Reactions

Chinese Journal of Organic Chemistry, Journal Year: 2025, Volume and Issue: 45(2), P. 641 - 641

Published: Jan. 1, 2025

Language: Английский

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Catalytic acceptorless dehydrogenation of alcohols using cobalt(i) pincer complexes supported by a P–GeH–P ligand

Chemical Communications, Journal Year: 2025, Volume and Issue: unknown

Published: Jan. 1, 2025

We report a novel P–GeH–P pincer ligand and its cobalt( i ) complex, which catalyzes the acceptorless dehydrogenation of alcohols.

Language: Английский

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Recent Advances on the Chemistry of Transition Metal Complexes with Monoanionic Bidentate Silyl Ligands

ChemPlusChem, Journal Year: 2024, Volume and Issue: unknown

Published: May 23, 2024

The chemistry of transition-metal (TM) complexes with monoanionic bidentate (κ

Language: Английский

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Coordination chemistry of ligands bearing heavy group 14 and 15 elements: Comparative analysis of their influence on transition metal chemistry

Coordination Chemistry Reviews, Journal Year: 2024, Volume and Issue: 526, P. 216317 - 216317

Published: Dec. 3, 2024

Language: Английский

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Cross-Dehydrogenative Coupling of Secondary Amines with Silanes Catalyzed by Agostic Iridium-NSi Species

Inorganic Chemistry, Journal Year: 2024, Volume and Issue: 64(1), P. 255 - 267

Published: Dec. 23, 2024

An active catalytic system for the cross-dehydrogenative coupling (CDC) of a wide range secondary amines with silanes is reported. The iridium(III) derivatives [Ir(H)(X)(κ2-NSiDMQ)(L)] (NSiDMQ = {4,8-dimethylquinoline-2-yloxy}dimethylsilyl; L coe, X Cl, 2; OTf, 3; PCy3, 4; 5), which are stabilized by weak yet noticeable Ir···H–C agostic interaction between iridium and one C–H bonds 8-Me substituent NSiDMQ ligand, have been prepared fully characterized. These species proven to be effective catalysts CDC hydrosilanes. best performance (TOF1/2 79,300 h–1) was obtained using 5 (0.25 mol %), N-methylaniline, HSiMe2Ph. activity [Ir(H)(OTf)(κ2-NSiQ)(PCy3)] (10, NSiQ {quinoline-2-yloxy}dimethylsilyl) [Ir(H)(OTf)(κ2-NSiMQ)(PCy3)] (11, NSiMQ {4-methylquinoline-2-yloxy}dimethylsilyl), related but lacking substituent, markedly lower than that found 5. This fact highlights crucial role ligand in enhancing these complexes.

Language: Английский

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Forging of silaoxycarbocyclics by interrupted Catellani reaction

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: unknown, P. 110474 - 110474

Published: Sept. 1, 2024

Language: Английский

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Theoretical study of the structure and stability of silyl cations with lewis bases using DFT and NBO analysis

STUDIES IN ENGINEERING AND EXACT SCIENCES, Journal Year: 2024, Volume and Issue: 5(3), P. e12703 - e12703

Published: Dec. 26, 2024

This study investigates the intricate interplay between electronic and steric factors in shaping Si-P bond lengths, angles, binding energies, charge distribution, interaction energies silicon-centered cation-phosphine base systems. A detailed analysis reveals that (CH₃)₃Si⁺ exhibits shortest lengths (2.01–2.03 Å), attributed to minimal hindrance favorable overlap. In contrast, (C₂H₅)₃Si⁺ displays slightly longer (2.03–2.05 while longest are observed Ar₃Si⁺ (2.08–2.10 due combined electron-withdrawing nature effects of aromatic groups. Variations angles further demonstrate influence bulk effects, with (C₂H₅)₃P consistently exhibiting larger (e.g., 120°–121° for Ar₃Si⁺) compared (CH₃)₃P. Binding energy calculations identify most (-28 kcal/mol) (CH₃)₃P, driven by an optimal balance geometry distribution. Charge transfer indicates donates more electron density than consistent trends expected from considerations. Natural Bond Orbital (NBO) confirms a strong negative correlation σ-donation energy, increased leading stronger interaction, which negative. weaker interactions its These findings underscore critical role defining strengths, providing valuable insights designing tailored silicon-phosphine complexes potential applications catalysis material sciences.

Language: Английский

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Complejos con ligandos sililo polidentados como catalizadores homogéneos en reacciones de hidrogenación e hidrosililación

Deleted Journal, Journal Year: 2024, Volume and Issue: 120(4), P. 192 - 192

Published: Dec. 26, 2024

La química de los complejos metales transición con ligandos monoaniónicos bidentados k2-Si,L y/o tridentados k3-Si,L2—donde Si simboliza un grupo sililo y L grupos neutros dadores s par electrones—ha despertado interés creciente en últimos años. Esta revisión presenta principales avances logrados la aplicación estos como catalizadores procesos clave, son hidrogenación hidrosililación moléculas insaturadas.

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