Computational Study Illustrating NCN-Palladium(IV) Involvement in Generating Pd0 Species to Facilitate Pd0/PdII Heck-Type Catalysis with Diphenyliodine(III) Species DOI
Allan J. Canty, Alireza Ariafard

Organometallics, Journal Year: 2023, Volume and Issue: 42(22), P. 3227 - 3235

Published: Nov. 8, 2023

Density functional theory has been applied in a mechanistic study of the role pincer complex PdII(NCN–N,C,N)(O2CPh-O) ([NCN]- = [2,6-(Me2NCH2)2C6H3]−) (3) Heck-type catalysis presence diphenyliodine(III) triflate as oxidative arylating agent for CH2═CHAr and bicarbonate base to afford PhCH═CHAr (Ar p-BrC6H4). The initially formed palladium(IV) PhPd(NCN–N,C,N)(OBz···HOCO2–O,O) (9) (ΔG‡ 31.6 kcal/mol) undergoes Ph···Cipso reductive elimination form PdII{NC(Ph)N–N,C,N}(OBz···HOCO2–O,O) (11) 25.6 kcal/mol), which is reduced by palladium(0) species. Reduction Pd0 occurs via deprotonation one NMe2 group provide "–CH2–N(Me)–CH2–PdII″ moiety 23.6 followed nucleophilic attack on this give product with "–CH2–NMe(CH2OCO2H)″ 14.5 kcal/mol). exceptionally facile addition Ph2I(HCO3) 5.1 Modeling [Pd(benzene)(O2CPh)]− provides similar result 5.6 allowing entry PhPdII species be able undergo migratory insertion CH2═CAr 14.4 β-hydride 16.2 processes Pd0/PdII catalysis. Activation barriers reduction PdIV Pd0, process, are lower than initial oxidation species, ensuring that only small quantity PdII(NCN)(OBz) consumed, accord its completion Computational studies PdIV-mediated revealed energetically unfavorable preference formation CH2═C(Ar)Ph rather experimentally reported PhCH═CHAr. This reveals precatalyst, PdII elimination, reducing extremely diaryliodine(III) reagent selectivity differences centers.

Language: Английский

Enantioselective Synthesis of Ferrocene 1,3-Derivatives via Palladium/Norbornene Cooperative Catalysis DOI

Princi Gupta,

Prakash C. Tiwari,

Suchithra Madhavan

et al.

ACS Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 17460 - 17468

Published: Nov. 12, 2024

Herein, we report a regio-and stereoselective distal C–H functionalization protocol for ferrocenes, leading to the synthesis of planar chiral ferrocene-1,3-derivatives by Catellani-type reaction. The successful Pd(II)/norbornene catalyst combination can reach inaccessible reaction site ferrocene and accomplishes selective C(3)-arylation ferrocenyl methylamine. ligand-controlled synergistic Pd/norbornene metal–organic cooperative catalysis under aerobic conditions successfully provides an array in moderate-to-good yields with good enantio- diastereoselectivities. A unique class 1,3-ligands, including PPFA-like pincer type ligands bearing central chirality, has been synthesized following this synthetic methodology.

Language: Английский

Citations

0
Chiral metal complexes: Design strategies for precision in asymmetric C–H activation DOI
Devesh Chandra,

T. SHARMA,

Sarthi

et al.

Journal of Catalysis, Journal Year: 2024, Volume and Issue: unknown, P. 115756 - 115756

Published: Sept. 1, 2024

Language: Английский

Citations

0
A Monoanionic Pincer Ligand with Pendant Phosphazene Arms: Stabilization of Main‐Group and Transition Metal Complexes DOI
Kunlong Li, Minghao Huang, Jiliang Zhou

et al.

European Journal of Inorganic Chemistry, Journal Year: 2023, Volume and Issue: 27(2)

Published: Oct. 27, 2023

Abstract An unprecedented anionic pincer ligand with pendant phosphazene arms [2,6‐(MesN=PPh 2 ) C 5 H 4 N] − ( L has been synthesized through a facile reaction of bis(iminophosphoranyl)‐pyridine K‐selectride. can stabilize main‐group and transition metal complexes GeCl, SnCl, ZnCl, CdI. X‐ray diffraction analysis theoretical study show that the strongly coordinate to centers, while central amide group alternatively donates one or two pairs electrons bind different centers.

Language: Английский

Citations

0
Computational Study Illustrating NCN-Palladium(IV) Involvement in Generating Pd0 Species to Facilitate Pd0/PdII Heck-Type Catalysis with Diphenyliodine(III) Species DOI
Allan J. Canty, Alireza Ariafard

Organometallics, Journal Year: 2023, Volume and Issue: 42(22), P. 3227 - 3235

Published: Nov. 8, 2023

Density functional theory has been applied in a mechanistic study of the role pincer complex PdII(NCN–N,C,N)(O2CPh-O) ([NCN]- = [2,6-(Me2NCH2)2C6H3]−) (3) Heck-type catalysis presence diphenyliodine(III) triflate as oxidative arylating agent for CH2═CHAr and bicarbonate base to afford PhCH═CHAr (Ar p-BrC6H4). The initially formed palladium(IV) PhPd(NCN–N,C,N)(OBz···HOCO2–O,O) (9) (ΔG‡ 31.6 kcal/mol) undergoes Ph···Cipso reductive elimination form PdII{NC(Ph)N–N,C,N}(OBz···HOCO2–O,O) (11) 25.6 kcal/mol), which is reduced by palladium(0) species. Reduction Pd0 occurs via deprotonation one NMe2 group provide "–CH2–N(Me)–CH2–PdII″ moiety 23.6 followed nucleophilic attack on this give product with "–CH2–NMe(CH2OCO2H)″ 14.5 kcal/mol). exceptionally facile addition Ph2I(HCO3) 5.1 Modeling [Pd(benzene)(O2CPh)]− provides similar result 5.6 allowing entry PhPdII species be able undergo migratory insertion CH2═CAr 14.4 β-hydride 16.2 processes Pd0/PdII catalysis. Activation barriers reduction PdIV Pd0, process, are lower than initial oxidation species, ensuring that only small quantity PdII(NCN)(OBz) consumed, accord its completion Computational studies PdIV-mediated revealed energetically unfavorable preference formation CH2═C(Ar)Ph rather experimentally reported PhCH═CHAr. This reveals precatalyst, PdII elimination, reducing extremely diaryliodine(III) reagent selectivity differences centers.

Language: Английский

Citations

0