Palladium Bisphosphine Monoxide Complexes: Synthesis, Scope, Mechanism, and Catalytic Relevance

Journal of the American Chemical Society, Journal Year: 2024, Volume and Issue: unknown

Published: Dec. 17, 2024

Recent studies in transition metal catalysis employing chelating phosphines have suggested a role for partial ligand oxidation formation of the catalytically active species, with potentially widespread relevance number catalytic systems. We examine internal redox reaction PdII(bisphosphine)X2 (X = Cl, OAc, etc.) complexes to reveal previously underexplored aspects bisphosphine monoxides (BPMOs), including evaluation structure and development general conditions access collection structurally diverse BPMO precatalysts based on organopalladium oxidative addition complexes. In particular, series PdII(BPMO)(R)(X) (R aryl, alkyl; X I, Br) bearing 24 different ligands were characterized by NMR X-ray crystallography. Comparison performance versus as is demonstrated be an enabling diagnostic tool Pd development. Finally, differences behavior between monoxide rationalized through solid-state parametrization stoichiometric experiments.

Language: Английский

---

Palladium Bisphosphine Mono-Oxide Complexes: Synthesis, Scope, Mechanism, and Catalytic Relevance

Published: Aug. 7, 2024

Recent studies in transition metal catalysis employing chelating phosphines have suggested a role for partial ligand oxidation formation of the catalytically active species, with potentially widespread relevance number cata-lytic systems. We examine internal redox reaction PdII(bisphosphine)X2 (X = Cl, OAc, etc.) complexes to reveal previously underexplored aspects bisphosphine mono-oxides (BPMOs), including evaluation structure and development general conditions access collection structurally diverse BPMO precatalysts based on organopalladium oxidative addition complexes. In particular, series PdII(BPMO)(R)(X) (R=Aryl, Alkyl; X=I, Br) bearing 24 different ligands were characterized by NMR X-ray crystallog-raphy. Comparison catalytic performance phosphine versus bisphos-phine as is demonstrated be an enabling diagnostic tool Pd develop-ment. Finally, differences behavior between mono-oxide rationalized through solid-state parametrization stoichiometric experiments.

Language: Английский

---

Diverse Catalytic Applications of Phosphine Oxide‐Based Metal Complexes

ChemCatChem, Journal Year: 2024, Volume and Issue: 16(22)

Published: Aug. 17, 2024

Abstract Phosphine oxides are an interesting class of compounds possessing tetracoordinate and pentavalent phosphorus atoms have been employed in a wide range applications including reagents organic synthesis, metal extractants, flame retardants, pharmaceuticals, bioactivity studies. Among all, the degree basicity phosphoryl oxygen driven by nature substituents influences electronic properties central complex toward diversified catalytic processes. Further, presence heteroatoms adjacent to atom enhances nucleophilicity atom. In view this, present review covers past two decades remarkable versatility P=O‐based complexes describes governing factors influencing structural resultant coordination behavior. Interestingly, some P=O bond distances either longer or shorter compared their free ligands, indicating activity. These can effectively catalyze chemical reactions polymerizations, C−C Si−C activations, oxidation, reduction, hydroformylation, hydrophosphination, hydrogenation cyclization reactions. Furthermore, this emphasizes impact substituents, solvents, additives, light, temperature on efficiency.

Language: Английский

---

Dehydrogenative α,γ-Diphosphinylation of Allylamines Enabled by Photoinduced Cobaloxime Catalysis

Organic Letters, Journal Year: 2024, Volume and Issue: unknown

Published: Nov. 18, 2024

A regioselective radical α,γ-diphosphinylation of allylamines with secondary phosphine oxides by photoinduced cobaloxime catalysis is described. The reaction tolerates a wide range and oxides, affording α-amino diphosphine dioxides in moderate to good yields hydrogen evolution. synthesis new monoxide ligands the promising antitumor activities products demonstrate great potential applications this approach drug discovery. detailed mechanism studies indicate that likely proceeds through dehydrogenative allylic phosphinylation nucleophilic addition process.

Language: Английский

---

Reactions of Alkynyl Aryl Phosphine Oxide with Oxalyl Bromide

Chinese Journal of Organic Chemistry, Journal Year: 2024, Volume and Issue: 44(12), P. 3753 - 3753

Published: Jan. 1, 2024

Language: Английский

---