Cooperative B–H Activation: Ligand Diversity in Groups 6 and 8 Transition Metal κ2-N,E-Chelated Complexes (E = S or Se) DOI

Suvam Saha,

Stutee Mohapatra,

Manish Kumar

et al.

Inorganic Chemistry, Journal Year: 2025, Volume and Issue: unknown

Published: Feb. 4, 2025

The synthesis, structure, and reactivity of the N-heterocyclic carbene (NHC)-supported κ2-N,S-chelated ruthenium complex [(IMe)(PPh3)Ru{κ2-N,S-(mbz)}2] (IMe = 1,3-dimethylimidazol-2-ylidene, mbz 2-mercaptobenzothiazolyl (NC7H4S2)), 2 has been established. Complex is generated from reaction [Ru(PPh3)2Cl2], 1 with IMe followed by addition [(mbz)K]. room-temperature [BH3·THF] led to formation dihydridoborate complex, [(Ph3P)Ru{κ3-H,S,S'-(NH2BSBH2N)(S2C7H4)2}], 3. Further, synthesis structure Cp*-supported tungsten complexes, [Cp*W(CO)2{κ2-N,S-(NC7H4S2)}], 5 [Cp*W(CO)2{κ2-N,S-(NC7H4S2)}{κ2-N,S-(N(CH3)C5H4S)}], 6, [Cp*W(CO)3Me], 4 [Na(H3B-NC7H4S2)] have described. In a similar fashion, pyridine-2-thiolato/selenolato ligand-supported Cp*-based κ2-N,E-chelated (E S Se) [Cp*W(CO)2{κ2-N,E-(NC5H4E)}] (7a: E (pyridine-2-thiolato), 7b: Se (pyridine-2-selenolato)), isolated [Na(H3B-NC5H4E)] ligands. bulky borane ArFBH2 (ArF 3,5-bistrifluoromethylbenzyl) isolation borate species, [Cp*W(CO)2{κ2-S,H-(H2ArFB-NC7H4S2)}], 10. [Cp*Mo(CO)2{κ2-N,Se-(NC5H4Se)}], 9 salt elimination [Cp*Mo(CO)3Cl], 8 [K(NC5H4Se)] reacts yield [Cp*Mo(CO)2{κ2-Se,H-(H3B-NC5H4Se)}], 11. To investigate effect ligand diversities on all density functional theory (DFT)-based calculations were performed.

Language: Английский

Strategies and mechanisms of metal–ligand cooperativity in first-row transition metal complex catalysts DOI
Matthew R. Elsby, R. Tom Baker

Chemical Society Reviews, Journal Year: 2020, Volume and Issue: 49(24), P. 8933 - 8987

Published: Jan. 1, 2020

The use of metal–ligand cooperation (MLC) by transition metal bifunctional catalysts has emerged at the forefront homogeneous catalysis science.

Language: Английский

Citations

242
Molecular Main Group Metal Hydrides DOI
Matthew M. D. Roy, Alvaro A. Omaña, Andrew S. S. Wilson

et al.

Chemical Reviews, Journal Year: 2021, Volume and Issue: 121(20), P. 12784 - 12965

Published: Aug. 27, 2021

This review serves to document advances in the synthesis, versatile bonding, and reactivity of molecular main group metal hydrides within Groups 1, 2, 12–16. Particular attention will be given emerging use said rapidly expanding field Main Group element-mediated catalysis. While this is comprehensive nature, focus research appearing open literature since 2001.

Language: Английский

Citations

213
Element‐Ligand Cooperativity with p‐Block Elements DOI Creative Commons
Lutz Greb, Fabian Ebner,

Yael Ginzburg

et al.

European Journal of Inorganic Chemistry, Journal Year: 2020, Volume and Issue: 2020(32), P. 3030 - 3047

Published: June 25, 2020

Metal‐ligand cooperativity (MLC) had a tremendous impact on d‐block metal‐mediated bond activation and homogeneous catalysis. Is this concept translatable to the elements of p‐block? Are there analogies already at hand? In review, we describe contributions in which p‐block element (group 13–15) its ligand (surrounding molecular framework) operate synergistically substrate or catalytic cycle. This activity is termed element‐ligand (ELC), correspondence MLC. After concepts low‐valent states frustrated Lewis pairs mimicking ambiphilic reactivity transition metals, spatial proximity nucleophilic electrophilic reaction sites small HOMO‐LUMO gap ELC complex might offer yet another approach. Selected examples shall illustrate common reactivities ELC, disclose conceptual with MLC, outline shortcomings field.

Language: Английский

Citations

89
Cooperativity in Transition Metal Tetrylene Complexes DOI Creative Commons
Rosie J. Somerville, Jesús Campos

European Journal of Inorganic Chemistry, Journal Year: 2021, Volume and Issue: 2021(34), P. 3488 - 3498

Published: Aug. 6, 2021

Cooperative reactivity between transition metals and ligands, or two metals, has created significant opportunities for the development of new transformations that would be difficult to carry out with a single metal. Here we explore cooperativity divalent heavier group 14 elements (tetrylenes), less-explored facet field cooperativity. Tetrylenes combine their strong σ-donor properties an empty p-orbital can accept electron density. This ambiphilicity allowed them form metal tetrylene metallotetrylene complexes place reactive site adjacent We have selected examples demonstrate what been achieved so far regarding cooperative reactivity, as this already spans metal-, tetrylene- multi-site-centred bond cleavage, cycloaddition, migration, metathesis, insertion. also highlight some challenges need overcome make it catalysis.

Language: Английский

Citations

58
Recent progress in transition metal complexes supported by multidentate ligands featuring group 13 and 14 elements as coordinating atoms DOI Creative Commons
Takashi Komuro, Yumiko Nakajima, Jun Takaya

et al.

Coordination Chemistry Reviews, Journal Year: 2022, Volume and Issue: 473, P. 214837 - 214837

Published: Oct. 1, 2022

Language: Английский

Citations

44
Cooperative Bond Activation and Catalytic CO2 Functionalization with a Geometrically Constrained Bis(silylene)-Stabilized Borylene DOI
Xi Chen, Yin Yang, Hao Wang

et al.

Journal of the American Chemical Society, Journal Year: 2023, Volume and Issue: 145(12), P. 7011 - 7020

Published: March 20, 2023

Metal–ligand cooperativity has emerged as an important strategy to tune the reactivity of transition-metal complexes for catalysis and activation small molecules. Studies main-group compounds, however, are scarce. Here, we report synthesis, structural characterization, a geometrically constrained bis(silylene)-stabilized borylene. The one-pot reaction [(SiNSi)Li(OEt2)] (SiNSi = 4,5-bis(silylene)-2,7,9,9-tetramethyl-9H-acridin-10-ide) with 1 equiv [BBr3(SMe2)] in toluene at room temperature followed by reduction 2 potassium graphite (KC8) leads borylene [(SiNSi)B] (1), isolated blue crystals 45% yield. X-ray crystallography shows that (1) tricoordinate boron center distorted T-shaped geometry. Computational studies reveal HOMO represents lone pair orbital on is delocalized over Si–B–Si unit, while geometric perturbation significantly increases its energy. Borylene single electron transfer toward tris(pentafluorophenyl)borane (B(C6F5)3), forming frustrated radical [(SiNSi)B]•+[B(C6F5)3]•–, which can be trapped PhSSPh, affording ion [(SiNSi)BSPh][PhSB(C6F5)3] (3). Remarkably, cooperation between silylene allows facile cleavage N–H bond aniline, P–P white phosphorus, C═O ketones carbon dioxide, thus representing new type element-ligand In addition, strikingly effective catalyst dioxide reduction. plays key role catalytic chemical process.

Language: Английский

Citations

32
Unlocking the potential of metal ligand cooperation for enantioselective transformations DOI Creative Commons
Tizian‐Frank Ramspoth, Johanan Kootstra, Syuzanna R. Harutyunyan

et al.

Chemical Society Reviews, Journal Year: 2024, Volume and Issue: 53(7), P. 3216 - 3223

Published: Jan. 1, 2024

Metal–ligand cooperation, (MLC) is a versatile catalysis concept. Herein, we discuss the historical context, mechanisms, and applications, suggesting exploring MLC for enantioselective transformations beyond (de)hydrogenative processes.

Language: Английский

Citations

11
Counterintuitive chemoselectivity in the reduction of carbonyl compounds DOI
Takanori Iwasaki, Kyoko Nozaki

Nature Reviews Chemistry, Journal Year: 2024, Volume and Issue: 8(7), P. 518 - 534

Published: June 3, 2024

Language: Английский

Citations

11
Calcium‐Ligand Cooperation Promoted Activation of N2O, Amine, and H2 as well as Catalytic Hydrogenation of Imines, Quinoline, and Alkenes DOI Creative Commons
Yaoyu Liang, Irena Efremenko, Yael Diskin‐Posner

et al.

Angewandte Chemie International Edition, Journal Year: 2024, Volume and Issue: 63(21)

Published: March 27, 2024

Abstract Bond activation and catalysis using s‐block metals are of great significance. Herein, a series calcium pincer complexes with deprotonated side arms have been prepared pyridine‐based PNP PNN ligands. The were characterized by NMR X‐ray crystal diffraction. Utilizing the obtained complexes, unprecedented N 2 O metal‐ligand cooperation (MLC) involving dearomatization‐aromatization pyridine ligand was achieved, generating aromatized diazotate as products. Additionally, dearomatized able to activate N−H bond well reversibly H , offering an opportunity for catalytic hydrogenation various unsaturated molecules. DFT calculations applied analyze electronic structures synthesized explore possible reaction mechanisms. This study is important complement area MLC main‐group metal chemistry.

Language: Английский

Citations

9
Controlled partial transfer hydrogenation of quinolines by cobalt-amido cooperative catalysis DOI Creative Commons
Maofu Pang, Jiayi Chen, Shengjie Zhang

et al.

Nature Communications, Journal Year: 2020, Volume and Issue: 11(1)

Published: March 6, 2020

Catalytic hydrogenation or transfer of quinolines was thought to be a direct strategy access dihydroquinolines. However, the challenge is control chemoselectivity and regioselectivity. Here we report an efficient partial system operated by cobalt-amido cooperative catalyst, which converts 1,2-dihydroquinolines reaction with H

Language: Английский

Citations

65