Iridium(2+), Triaqua[(1,2,3,4,5‐ η )‐1,2,3,4,5‐pentamethyl‐2,4‐cyclopentadien‐1‐yl]‐, Sulfate (1:1) (9CI, ACI)

Encyclopedia of Reagents for Organic Synthesis, Journal Year: 2025, Volume and Issue: unknown, P. 1 - 5

Published: Jan. 3, 2025

image [ 254734‐81‐1 ] C 10 H 21 IrO 7 S (MW 477.5) InChI = 1S/C10H15.Ir.H2O4S.3H2O/c1‐6‐7(2)9(4)10(5)8(6)3;;1‐5(2,3)4;;;/h1‐5H3;;(H2,1,2,3,4);3*1H2/q;+3;;;;/p‐2 InChIKey GJRJDFVEUYVULE‐UHFFFAOYSA‐L (the reagent is an iridium aqua complex used for transfer hydrogenations; simple tripeptides are versatile ligands affording water‐soluble catalysts and also accelerate the reduction transformations; moreover, ligation to peptides enables asymmetric hydrogenation reactions) Alternate Names: [Ir(pentamethylcyclopentadiene)(H 2 O) 3 ]SO 4 ; [IrCp * (H [(η (5) ‐C 5 Me )Ir(III)(H [Ir(III)(η ‐pentamethylcyclopentadienyl)(H ](SO ); [(pentamet hylcyclopentadienyl)iridium(III)(H [Ir(η ‐pentamethylcylopentadienyl)(water) . Physical Data: yellow, pale or orange solid. 1 Solubility: sol O (300 g L −1 ) at 25 °C. 1a,2 Preparative Method: iridium(2+), triaqua[(1,2,3,4,5‐)‐1,2,3,4,5‐pentamethyl‐2,4‐cyclopentadien‐1‐yl]‐, sulfate (1:1) can be prepared by treatment of pentamethylcyclopentadienyliridium(III) chloride dimer with silver sulfate. The diiridium could synthesized refluxing pentamethylcyclopentadiene in methanol (eq 1). 1b Alternatively, may hexachloroiridium 2) heating ‐pentamethylcyclopentadienyl)IrH carbon tetrachloride benzene 3). Other methods synthesize involve several complexes hydrogen gas (eqs 6 , 8 ). Handling, Storage, Precautions: preferably stored under inert atmosphere.

Language: Английский

---

Heterogeneous Mn@CeO₂ Catalyst for α-Alkylation of Ketones with Alcohols via Hydrogen-Borrowing Strategy

ACS Omega, Journal Year: 2025, Volume and Issue: 10(9), P. 9649 - 9660

Published: Feb. 24, 2025

Construction of a C-C bond via alkylation ketones with alcohol as the alkylating source by employing hydrogen-borrowing strategy is attracting significant attention and highly appealing due to its simplicity, cost-effectiveness, environmental benefits, fact that water only byproduct. The development heterogeneous catalysts based on nonprecious base metals progressing rapidly. Our newly disclosed manganese-doped cerium oxide nanocomposite (10 wt % Mn@CeO2) stands out cost-efficient air-stable catalyst, synthesized through straightforward coprecipitation method employed for α-alkylation primary alcohols strategy. X-ray diffraction (XRD) analysis confirms high crystallinity CeO2, while field emission scanning electron microscopy (FE-SEM) high-resolution transmission (HR-TEM) images reveal MnO2 nanoparticles, measuring 19 nm in size, uniformly decorated rod-shaped CeO2 which have size 33 nm. photoelectron spectroscopy (XPS) uncovers presence Mn4+ species embedded nanorods. Electron paramagnetic resonance (EPR) further indicates surface defects contribute impressive catalytic yield, ranges from 70 98% α-alkylated ketones. Thermogravimetric (TGA) demonstrates remarkable thermal stability maintaining up 800 °C. Additionally, inductively coupled plasma mass spectrometry (ICP-MS) no leaching Mn ions, emphasizing heterogeneity catalyst. Remarkably, 10 Mn@CeO2 recycled six cycles loss activity. This study underscores synergistic effect between metal redox pair key exceptional activity reactions, making promising catalyst sustainable efficient formation.

Language: Английский

---

Ruthenium-catalyzed β-alkylation of secondary alcohols with primary alcohols: Protic N-heterocyclic carbene's promotional influence

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: 1305, P. 137815 - 137815

Published: Feb. 17, 2024

Language: Английский

---

Mechanistic Insights into a Co(II)-Coordinated “Free” Metal Site of 2D Zinc-Based MOFs for β-Alkylation of Secondary Alcohols with Primary Alcohols

Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 62(45), P. 18689 - 18696

Published: Oct. 28, 2023

Through in-depth study of the properties and reaction mechanisms catalysts, it is possible to better optimize catalytic systems improve efficiency selectivity. This remains one challenges in field catalysis. Therefore, research design catalysts play crucial roles understanding optimizing mechanisms. A robust 2D zinc-based MOFs (Zn-HA) supported Co(II) ion catalyst (Zn-HA@Co) has been designed synthesized via a coordination-assisted strategy for β-alkylation secondary alcohols with primary alcohols. The characterization demonstrated that anchoring on Zn-HA coordination could efficiently enhance dispersity interaction between MOFs. Importantly, density functional theory results have provided mechanistic insights into energy HOMO LUMO Zn-HA@Co as well change entire process after interacting reactants specific changes each orbital. effectively lower barrier process. We expect our will serve valuable guideline

Language: Английский

---

Bimetallic Ru(II) Complex Catalysed β‐Alkylation of Secondary Alcohols and α‐Alkylation of Ketones: Selective Formation of Saturated Ketones

European Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 27(24)

Published: March 29, 2024

Abstract Ru(II) bimetallic [( p ‐cymene) 2 (RuCl) L 1 ]2X (X=BF 4 ( Cat2 ); X=PF 6 Cat3 )) and monometallic ‐cymene)(RuCl)L ]BF Cat4 ) (where =N,N’‐(3,3’,5,5’‐tetraisopropyl‐[1,1’‐biphenyl]‐4,4’‐diyl)bis(1‐(pyridin‐2‐yl)methanimine); =N‐(2,6‐diisopropyl‐phenyl)‐1‐(pyridin‐2‐yl)‐methanimine) catalyse selective synthesis of saturated ketones using β‐alkylation secondary alcohol or α‐alkylation with primary alcohol. Notably, a single catalyst facilitates the oxidation both alcohols followed by condensation hydrogenation yielding α‐alkylated ketones. Remarkably, this system allows loading as low 0.01 mol% for 0.005 ketone, delivering access to wide array derivatives yields ~97 %. Complex , in particular, orchestrates one‐pot alkylation reactions high turnover frequency (TOF) 5.6 10 5 h −1 0.0001 mol%. A comparative study between complexes reveals that complex exhibits better selectivity formation presumably owing cooperative effect metal centres. The scale‐up highlights practical applicability catalytic approach. To delve into plausible mechanisms, we conducted initial investigations through meticulously controlled experiments spectroscopic analysis.

Language: Английский

---

Efficient Synthesis of Benzimidazole and Quinoline Derivatives Catalyzed by Functionalized Amidato Ruthenium Complexes in Water via Acceptorless Dehydrogenative Coupling Strategy

ChemCatChem, Journal Year: 2023, Volume and Issue: 15(16)

Published: July 10, 2023

Abstract Transition‐metal‐catalyzed acceptorless dehydrogenative coupling (ADC) has emerged as a sustainable synthetic strategy for the construction of N ‐heteroaromatics. Herein, series water‐soluble amidato Ru catalysts were designed, synthesized, and utilized in selective synthesis 2‐substituted benzimidazoles from aromatic diamines primary alcohols, well quinolines substituted 2‐aminobenzyl alcohols acetophenones via ADC water. Catalyst 1 d bearing strong electron‐donating hydroxyl group on ligand exhibited best catalytic activity. The system demonstrated remarkable efficiency versatility, allowing application over 40 substrates two reactions with good to high yields. Based control experiments density functional theory (DFT) calculations, plausible mechanism was proposed, highlighting significant role functionalized complexes catalyzing alcohol dehydrogenation an outer‐sphere pathway.

Language: Английский

---

N,N-Dialkylation of Acyl Hydrazides with Alcohols Catalyzed by Amidato Iridium Complexes via Borrowing Hydrogen

Organometallics, Journal Year: 2023, Volume and Issue: 42(18), P. 2623 - 2631

Published: April 1, 2023

Direct N,N-dialkylation of acyl hydrazide catalyzed by a series amidato iridium complexes bearing an electron-donating group in the ligand using methanol or ethanol as alkyl reagent under weak base conditions (10 mol % KHCO3) is described. A wide range derivatives are converted to corresponding N,N-dialkylated products excellent yields (38 examples, ≤96%). On basis control experiments and nuclear magnetic resonance studies, plausible mechanism was proposed. The experimental results indicate that ortho groups on phenyl moiety picolinamide play crucial role catalytic activity.

Language: Английский

---

Metal-free construction of diverse 1,2,4-triazolo[1,5-a]pyridines on water

Chinese Chemical Letters, Journal Year: 2024, Volume and Issue: 36(1), P. 109755 - 109755

Published: March 9, 2024

Language: Английский

---

Synthesis and reactivity of isomeric Ru complexes with hydroxypyridyl fragment: active catalysts for β‑alkylation of secondary alcohols with primary alcohols

Journal of Molecular Structure, Journal Year: 2024, Volume and Issue: 1321, P. 140159 - 140159

Published: Sept. 23, 2024

Language: Английский

---