Metallated Container Molecules: A Capsular Nickel Catalyst for Enhanced Butadiene Polymerisation

Elaieb, Fethi; Sameni, Soheila; Awada, Mouhamad; Jeunesse, Catherine; Matt, Dominique; Toupet, Loı̈c; Harrowfield, Jack; Takeuchi, Daisuke; Takano, Shigenaga

doi:10.1002/ejic.201901074

Cited by 3 publications

(1 citation statement)

References 49 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Another ligand conceived as an effective source for metal confinement is the long diphosphine 66 (Figure 14) which features two bridged conical calixarene subunits. The authors anticipated that upon chelation of metal cations having two cis ‐disposed, free coordination sites, 66 would not only adopt a rigid, capsular form (by bringing the two conical parts together), but also confine the coordinated metal centre inside the resulting container [49] . This occurred, for example, when mixing 66 with [Ni(η 5 ‐C 5 H 5 )(cod)]BF 4 (cod=1,5‐cyclooctadiene), a reaction leading quantitatively to capsule 67 , characterised by a structure determination showing an embedded nickel atom and two large entries.…”

Section: Cavity‐supported P(iii) Ligands As a Tool For Metal Confinementmentioning

confidence: 99%

Phosphines and other P(III)‐derivatives with Cavity‐shaped Subunits: Valuable Ligands for Supramolecular Metal Catalysis, Metal Confinement and Subtle Steric Control

Matt

Harrowfield

2020

ChemCatChem

Self Cite

View full text Add to dashboard Cite

Tertiary phosphines and other P(III)‐derivatives are the par excellence ligands in industrially relevant homogeneous catalysis. A promising, recent development in this field concerns the use of P(III)‐compounds that incorporate cavity‐shaped subunits capable of assisting metal‐centred reactions, either by functioning as receptor moieties, creating confinement about the reactive centre or merely by influencing main catalytic steps via strong steric interactions exerted on the metal first coordination sphere. This Minireview, which is based on selected examples, illustrates the utility of covalently‐constructed phosphines that incorporate a cavity and highlights future directions that deserve development in ligand design.

show abstract

Section: Cavity‐supported P(iii) Ligands As a Tool For Metal Confinementmentioning

confidence: 99%

Phosphines and other P(III)‐derivatives with Cavity‐shaped Subunits: Valuable Ligands for Supramolecular Metal Catalysis, Metal Confinement and Subtle Steric Control

Matt

Harrowfield

2020

ChemCatChem

Self Cite

View full text Add to dashboard Cite

show abstract

Encapsulated Neutral Ruthenium Catalyst for Substrate‐Selective Oxidation of Alcohols

Hkiri

Steinmetz

Schurhammer

et al. 2022

Chemistry A European J

View full text Add to dashboard Cite

The neutral complex dichloro-{diethyl [(5-phenyl-1,3,4-oxadiazol-2-ylamino)-(4-trifluoro-methylphenyl)methyl]phosphonate} (p-cymene)-ruthenium(II) was encapsulated inside a self-assembled hexameric host obtained upon reaction of 2,8,14,20-tetra-undecyl-resorcin[4]arene and water. The formation of an inclusion complex was inferred from a combination of spectral measurements (MS, UV/Vis spectroscopy, 1 H and DOSY NMR). The 31 P and 19 F NMR spectra are consistent with motions of the ruthenium complex inside the self-assembled capsule. Molecular dynamics simulations carried out on the inclusion complex confirmed these intracavity movements and highlighted possible supramolecular interactions between the ruthenium first coordination sphere ligands and the inner part (aromatic rings) of the capsule. The embedded ruthenium complex was assessed in the catalytic oxidation (using NaIO 4 as oxidant) of mixtures of three arylmethyl alcohols into the corresponding aldehydes. The reaction kinetics were shown to vary as a function of the substrates' size, with the oxidation rate varying in the order benzylalcohol > 4-phenyl-benzylalcohol > 9-anthracenemethanol. Control experiments realized in the absence of hexameric capsule did not allow any discrimination between the substrates.

show abstract

Cyclopentadienyl Nickel Complexes

Włodzimierz

2022

Comprehensive Organometallic Chemistry IV

View full text Add to dashboard Cite

Metallated Container Molecules: A Capsular Nickel Catalyst for Enhanced Butadiene Polymerisation

Abstract: A unique, covalently constructed capsular catalyst obtained by reaction of [Ni(η 5 -C 5 H 5 )(1,5-cyclooctadiene)] BF 4 with the double-calixarene-derived diphosphine 1,3-bis (5-diphenylphosphino-25,26,27,28-tetrapropoxycalix[4]aren-17-yl)- [a]

Cited by 3 publications

References 49 publications

Phosphines and other P(III)‐derivatives with Cavity‐shaped Subunits: Valuable Ligands for Supramolecular Metal Catalysis, Metal Confinement and Subtle Steric Control

Phosphines and other P(III)‐derivatives with Cavity‐shaped Subunits: Valuable Ligands for Supramolecular Metal Catalysis, Metal Confinement and Subtle Steric Control

Encapsulated Neutral Ruthenium Catalyst for Substrate‐Selective Oxidation of Alcohols

Cyclopentadienyl Nickel Complexes

Contact Info

Product

Resources

About