Ylide-Functionalized Phosphine (YPhos) Platinum Complexes: Synthesis and Application in Hydrosilylations under Mild Conditions

Rodstein, Ilja; Doppiu, Angelino; Gessner, Viktoria H.

doi:10.1021/acs.organomet.3c00156

Increasing the Donor Strength of Alkenylphosphines by Twisting the C=C Double Bond

Yu,

Hsiao,

Löffler

et al. 2024

Angewandte Chemie

0

View full text Add to dashboard Cite

Electron‐rich phosphines play a crucial role in transition metal‐based homogeneous catalysis. While alkyl groups have traditionally been employed to increase the phosphine donor strength, recent studies have shown that zwitterionic functional groups such as phosphorus ylides can result in a further enhancement. Herein we report the concept of twisting a C=C double bond to introduce a zwitterionic substituent by the synthesis and application of N‐heterocyclic olefin phosphines with a sulfonyl substituent (sNHOP). This sulfonyl group enables the twisting of the olefin moiety due to steric and electronic stabilization of the carbanionic center. The resulting zwitterionic structure leads to a significant increase of the donor strength of the sNHOP ligands compared to conventional NHOP systems with a planar N‐heterocyclic olefin moiety. The potential of this new ligand platform for catalysis is demonstrated by its application in the gold‐catalyzed hydroamination and cyclo‐isomerization of alkynes. Here, the ligands outperform the original NHOP ligands suggesting favorable properties for future catalysis applications.

show abstract

Increasing the Donor Strength of Alkenylphosphines by Twisting the C=C Double Bond

Yu,

Hsiao,

Löffler

et al. 2024

Angew Chem Int Ed

0

View full text Add to dashboard Cite

Electron‐rich phosphines play a crucial role in transition metal‐based homogeneous catalysis. While alkyl groups have traditionally been employed to increase the phosphine donor strength, recent studies have shown that zwitterionic functional groups such as phosphorus ylides can result in a further enhancement. Herein we report the concept of twisting a C=C double bond to introduce a zwitterionic substituent by the synthesis and application of N‐heterocyclic olefin phosphines with a sulfonyl substituent (sNHOP). This sulfonyl group enables the twisting of the olefin moiety due to steric and electronic stabilization of the carbanionic center. The resulting zwitterionic structure leads to a significant increase of the donor strength of the sNHOP ligands compared to conventional NHOP systems with a planar N‐heterocyclic olefin moiety. The potential of this new ligand platform for catalysis is demonstrated by its application in the gold‐catalyzed hydroamination and cyclo‐isomerization of alkynes. Here, the ligands outperform the original NHOP ligands suggesting favorable properties for future catalysis applications.

show abstract

Influence of Ylide Functionalization on the Catalytic Performance of Ferrocenyldiphosphines in Au(I)‐Catalyzed Hydroaminations and Hydrohydrazinations

Duari,

Sarbajna,

Yu

et al. 2024

ChemCatChem

0

View full text Add to dashboard Cite

Ylide‐functionalized phosphines (YPhos) have been shown to yield highly active gold catalysts owing to their high donor capacity. To examine the impact of ylide functionalization on a given ligand structure, a series of ferrocenyl diphosphines functionalized with no, one or two ylide moieties and their corresponding bimetallic gold complexes were prepared. The complexes feature an anti‐conformation of the two phosphine moieties, guaranteeing the presence of two independent metal centers. Comparative studies of the complexes in the hydroamination and hydrohydrazination of alkynes revealed a significant increase in catalytic activity for each newly introduced ylide group. The di‐YPhos ligands were revealed to be the most active precatalysts, functioning effectively even at 0.1 or 0.2 mol% catalyst loading. This catalytic efficiency was demonstrated for a series of alkynes, amines and hydrazines.

show abstract

Ylide-Functionalized Phosphine (YPhos) Platinum Complexes: Synthesis and Application in Hydrosilylations under Mild Conditions

Cited by 6 publications

References 50 publications

Increasing the Donor Strength of Alkenylphosphines by Twisting the C=C Double Bond

Increasing the Donor Strength of Alkenylphosphines by Twisting the C=C Double Bond

Increasing the Donor Strength of Alkenylphosphines by Twisting the C=C Double Bond

Influence of Ylide Functionalization on the Catalytic Performance of Ferrocenyldiphosphines in Au(I)‐Catalyzed Hydroaminations and Hydrohydrazinations

Contact Info

Product

Resources

About