Complejos con ligandos sililo polidentados como catalizadores homogéneos en reacciones de hidrogenación e hidrosililación DOI Creative Commons
Francisco J. Fernández‐Álvarez

Deleted Journal, Год журнала: 2024, Номер 120(4), С. 192 - 192

Опубликована: Дек. 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.

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

Yicong Ge,

Jie Ke, Chuan He

и другие.

Accounts of Chemical Research, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

Процитировано

1

Recent Advances on the Chemistry of Transition Metal Complexes with Monoanionic Bidentate Silyl Ligands DOI Creative Commons
María Batuecas, Alejandra Goméz‐España, Francisco J. Fernández‐Álvarez

и другие.

ChemPlusChem, Год журнала: 2024, Номер unknown

Опубликована: Май 23, 2024

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

Язык: Английский

Процитировано

3

Rhodium(III)‐NSi Catalyzed Styrene Hydrosilylation: Evidence of the Hemilabile Character of NSi‐type Ligands DOI Open Access
Francisco J. Fernández‐Álvarez, Alejandra Goméz‐España, Marina Padilla

и другие.

Chemistry - A European Journal, Год журнала: 2025, Номер unknown

Опубликована: Янв. 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.

Язык: Английский

Процитировано

0

X-Type Silyl Ligands Mediated C—H Functionalization Reactions DOI

Jihui Gao,

Chuan He

Chinese Journal of Organic Chemistry, Год журнала: 2025, Номер 45(2), С. 641 - 641

Опубликована: Янв. 1, 2025

Язык: Английский

Процитировано

0

Catalytic acceptorless dehydrogenation of alcohols using cobalt(i) pincer complexes supported by a P–GeH–P ligand DOI
Yu‐Chao Liu, Danyan Cao,

Qi-Yang Ban

и другие.

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

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

Язык: Английский

Процитировано

0

Discrete Metal Clusters Supported by Heavier Group-14-Element Ligands DOI Creative Commons
Yusuke Sunada

Coordination chemistry research., Год журнала: 2025, Номер unknown, С. 100007 - 100007

Опубликована: Май 1, 2025

Язык: Английский

Процитировано

0

Permethylated Silicon: A Structural Motif with a Critical Role in Shaping the Properties of Organic–Inorganic Compounds DOI Creative Commons
Maria Cazacu, Madalin Damoc, Alexandru‐Constantin Stoica

и другие.

Journal of Inorganic and Organometallic Polymers and Materials, Год журнала: 2025, Номер unknown

Опубликована: Май 27, 2025

Язык: Английский

Процитировано

0

Seven‐Coordinate Ruthenium Complex with an SiNN‐Pincer Ligand as a Catalyst for Vinyl C─H Deuteration of Olefins DOI Creative Commons
Takashi Komuro,

Daiki Mochizuki,

Nozomu Ishiwata

и другие.

Chemistry - An Asian Journal, Год журнала: 2025, Номер unknown

Опубликована: Май 26, 2025

Abstract Seven‐coordinate ruthenium complexes 1a and 1b , featuring silyl–2,2´‐bipyridine SiNN‐pincer ligands with i ‐Pr t ‐Bu groups on Si, respectively, were synthesized. Their capped octahedral structures revealed by single‐crystal X‐ray diffraction study. The stoichiometric reactions of styrene in THF afforded η 2 ‐silylalkene chelate complexes. In contrast, performing the same reaction using C 6 D resulted liberation deuterated (PhDC═CD ), alongside formation a complex. Complex exhibited efficient catalytic activity for triple deuteration vinyl hydrogens mono‐substituted olefins to afford RDC═CD (R = Ph, H 4 ‐4‐OMe, ‐Bu) high deuterium incorporation (92%–99%D).

Язык: Английский

Процитировано

0

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

Yeong Jun Son,

Dongyoung Kim, Jae Wan Park

и другие.

Coordination Chemistry Reviews, Год журнала: 2024, Номер 526, С. 216317 - 216317

Опубликована: Дек. 3, 2024

Язык: Английский

Процитировано

2

Cross-Dehydrogenative Coupling of Secondary Amines with Silanes Catalyzed by Agostic Iridium-NSi Species DOI Creative Commons
Marina Padilla, María Batuecas, Pilar García‐Orduña

и другие.

Inorganic Chemistry, Год журнала: 2024, Номер 64(1), С. 255 - 267

Опубликована: Дек. 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.

Язык: Английский

Процитировано

1