Synthesis and Characterization of a Triphos Ligand Derivative and the Corresponding Pd<sup>II</sup> Complexes

Miller, Deanna L.; Boro, Brian J.; Grubel, Katarzyna; Helm, Monte L.; Appel, Aaron M.

doi:10.1002/ejic.201500791

Cited by 5 publications

(1 citation statement)

References 28 publications

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“…In addition to alkali metals, these host molecules are able to bind a wide range of ionic and neutral species [2–5], and have been utilized as chemical modulators in a wide range of ion-selective applications [2,4,6–10]. In transition metal (TM) chemistry, secondary coordination sphere modifications have become an important way of modulating stoichiometric and catalytic activity [11–14]. Secondary coordination sphere modifications of TMs involving control of simple cations and their interactions with TM-bound substrates are a relatively under-explored area.…”

Section: Introductionmentioning

confidence: 99%

Tridentate phosphine ligands bearing aza-crown ether lariats

2018

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Crown ethers are useful macrocycles that act as size-selective binding sites for alkali metals. These frameworks have been incorporated into a number of macromolecular assemblies that use simple cations as reporters and/or activity triggers. Incorporating crown ethers into secondary coordination sphere ligand frameworks for transition metal chemistry will lead to new potential methods for controlling bond formation steps, and routes that couple traditional ligand frameworks with these moieties are highly desirable. Herein we report the syntheses of a family of tridentate phosphine complexes bearing tethered aza-crown ethers (lariats) designed to modularize the variation of aza-crown size, lariat length, and distal phosphine substituents, followed by the synthesis and solid-state structures of Mo(III) complexes bearing cations in the pendent crown ethers.

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Section: Introductionmentioning

confidence: 99%

Tridentate phosphine ligands bearing aza-crown ether lariats

2018

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A P−P Bond as a Redox Reservoir and an Active Reaction Site

Kim

Lee

2018

Angewandte Chemie

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The carbonylation of a nickel(II) anilido species 2 led to the formation of a dinickel(0)–CO complex (P2P‐PP2){Ni(CO)}2 3 with a P−P bond along with isocyanate generation. In this reaction, the central phosphide moiety of an anionic PPP ligand (PPP−=−P[2‐PiPr2C6H4]2) acts as a single‐electron donor to form a P radical. Alternatively, 3 can be synthesized from the reduction of (PPP)NiCl (1) in the presence of CO; thus, the reaction proceeds by radical coupling of a .P−Ni0−CO species. The reverse reaction occurred to generate 1 when 3 was treated with AgCl. Since the P−P bond is light‐sensitive, its homolysis is possible and was explored by EPR spectroscopy and DFT analysis. Finally, various bond‐activation reactions of 3 occurred under visible‐light conditions, thus indicating that a P−P bond can act as an active reaction site.

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A P−P Bond as a Redox Reservoir and an Active Reaction Site

Kim

Lee

2018

Angew Chem Int Ed

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The carbonylation of a nickel(II) anilido species 2 led to the formation of a dinickel(0)-CO complex (P P-PP ){Ni(CO)} 3 with a P-P bond along with isocyanate generation. In this reaction, the central phosphide moiety of an anionic PPP ligand (PPP = P[2-P Pr C H ] ) acts as a single-electron donor to form a P radical. Alternatively, 3 can be synthesized from the reduction of (PPP)NiCl (1) in the presence of CO; thus, the reaction proceeds by radical coupling of a P-Ni -CO species. The reverse reaction occurred to generate 1 when 3 was treated with AgCl. Since the P-P bond is light-sensitive, its homolysis is possible and was explored by EPR spectroscopy and DFT analysis. Finally, various bond-activation reactions of 3 occurred under visible-light conditions, thus indicating that a P-P bond can act as an active reaction site.

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Synthesis and Characterization of a Triphos Ligand Derivative and the Corresponding Pd^II Complexes

Abstract: The synthesis of the new bis[2-(diphenylphosphino)ethyl]-(hydroxymethyl)phosphine tridentate ligand L CH2OH/Ph is reported. The ligand reacts with [Pd(Cl) 2 (PhCN) 2 ] to form [Pd(L CH2OH/Ph )Cl]Cl. Exchange of the chloride ions for triflate [a] Pacific

Cited by 5 publications

References 28 publications

Tridentate phosphine ligands bearing aza-crown ether lariats

Tridentate phosphine ligands bearing aza-crown ether lariats

A P−P Bond as a Redox Reservoir and an Active Reaction Site

A P−P Bond as a Redox Reservoir and an Active Reaction Site

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Synthesis and Characterization of a Triphos Ligand Derivative and the Corresponding PdII Complexes

Abstract: The synthesis of the new bis[2-(diphenylphosphino)ethyl]-(hydroxymethyl)phosphine tridentate ligand L CH2OH/Ph is reported. The ligand reacts with [Pd(Cl) 2 (PhCN) 2 ] to form [Pd(L CH2OH/Ph )Cl]Cl. Exchange of the chloride ions for triflate [a] Pacific

Cited by 5 publications

References 28 publications

Tridentate phosphine ligands bearing aza-crown ether lariats

Tridentate phosphine ligands bearing aza-crown ether lariats

A P−P Bond as a Redox Reservoir and an Active Reaction Site

A P−P Bond as a Redox Reservoir and an Active Reaction Site

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Synthesis and Characterization of a Triphos Ligand Derivative and the Corresponding Pd^II Complexes