Synthesis and Characterization of a New Binucleating Tetraphosphine Ligand Based on 1,2-Phenylene Chelates and the Structures of Dinickel Tetrachloride Complexes of the Ligand

Schreiter, William J.; Monteil, Alexandre R.; Kalachnikova, Ekaterina; Peterson, Marc Anthony; Moulis, Marshall D.; Gasery, Ciera D.; McCandless, Gregory T.; Fronczek, Frank R.; Stanley, George G.

doi:10.1021/ic5019345

Cited by 5 publications

(2 citation statements)

References 16 publications

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“…Alternatively, nucleophilic arylation of dialkylphosphinoyl chlorides (Scheme , B) and double nucleophilic addition of organometallic species to arylphosphoryl dichlorides and arylphosphonic acid esters (Scheme , C) have been described. In addition, P(III)-precursors like dialkylphosphinyl chlorides and aryldichlorophosphines are reported to react with C-nucleophiles (Scheme , D and E), and arylphosphines can be alkylated using alkyl halides (Scheme , F). However, when P(III) intermediates are employed, a subsequent oxidation of the intermediate tertiary phosphines to the phosphine oxides I is required.…”

Section: Resultsmentioning

confidence: 99%

Phosphine Oxides from a Medicinal Chemist’s Perspective: Physicochemical and in Vitro Parameters Relevant for Drug Discovery

2020

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Phosphine oxides and related phosphorus-containing functional groups such as phosphonates and phosphinates are established structural motifs that are still underrepresented in today’s drug discovery projects, and only few examples can be found among approved drugs. In this account, the physicochemical and in vitro properties of phosphine oxides and related phosphorus-containing functional groups are reported and compared to more commonly used structural motifs in drug discovery. Furthermore, the impact on the physicochemical properties of a real drug scaffold is exemplified by a series of phosphorus-containing analogs of imatinib. We demonstrate that phosphine oxides are highly polar functional groups leading to high solubility and metabolic stability but occasionally at the cost of reduced permeability. We conclude that phosphine oxides and related phosphorus-containing functional groups are valuable polar structural elements and that they deserve to be considered as a routine part of every medicinal chemist’s toolbox.

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Section: Resultsmentioning

confidence: 99%

Phosphine Oxides from a Medicinal Chemist’s Perspective: Physicochemical and in Vitro Parameters Relevant for Drug Discovery

2020

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“…Unfortunately, the dicationic dirhodium catalyst suffers from degradation pathways that lead to catalyst deactivation. A tetraphosphine ligand with a far stronger chelate effect was synthesized, and studies with model nickel complexes using both ligand diastereomers demonstrated the enhanced stability toward phosphine ligand dissociation (15).…”

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confidence: 99%

Highly active cationic cobalt(II) hydroformylation catalysts

Hood

Johnson

Carpenter

et al. 2020

Science

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125

140

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The cobalt complexes HCo(CO)4 and HCo(CO)3(PR3) were the original industrial catalysts used for the hydroformylation of alkenes through reaction with hydrogen and carbon monoxide to produce aldehydes. More recent and expensive rhodium-phosphine catalysts are hundreds of times more active and operate under considerably lower pressures. Cationic cobalt(II) bisphosphine hydrido-carbonyl catalysts that are far more active than traditional neutral cobalt(I) catalysts and approach rhodium catalysts in activity are reported here. These catalysts have low linear-to-branched (L:B) regioselectivity for simple linear alkenes. However, owing to their high alkene isomerization activity and increased steric effects due to the bisphosphine ligand, they have high L:B selectivities for internal alkenes with alkyl branches. These catalysts exhibit long lifetimes and substantial resistance to degradation reactions.

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Dimers and 2D Networks of Adamantane‐Related Ternary Organosilicon Coinage Metal Sulfide Clusters

Nier,

Rinn,

Guggolz

et al. 2024

Chemistry A European J

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Adamantane‐type organotin sulfide clusters were recently shown to react with coinage metal phosphine complexes under replacement of an organic substituent by a metal‐phosphine unit. An extension of such studies involving the silicon‐based congener [(PhSi)4S6] (A) revealed that the cluster core will be partly disassembled and a {PhSi} moiety is replaced by a coinage metal phosphine complex to form [(Et3PAg)3(PhSi)3S6] (B) and [Na2(thf)2.33][(Me3PCu)(PhSi)3S6] (C). Herein, we present an extension of this work upon variation of the reactants and reaction conditions. Besides the isolation of crystalline precursor complexes [CuCl(PMe2Ph)3] (1) and [AgCl(PMe2Ph)2]2 (2), the study addresses reactions of A with AgCl and a phosphine ligand in CH2Cl2, upon which A is completely disassembled to form [(Ph3P)3Ag(µ‐S)SiCl2Ph] (3). In another case a CH2 group, most likely stemming from CH2Cl2, was attached to the ligand, thus generating [{PhCl(S)SiSCH2P(Ph2)CH2CH2}2] (4). Upon using CuCl and 1,4‑bis(diphenylphosphino)butane (dppb) we isolated the phosphine‐bridged analog of B, [{(dppbCu2)CuP(Ph2)(CH2CH2)(PhSi)3S6}2] (5). In order to receive the yet elusive silver homolog of C, we used PMe2Ph as a bulkier ligand. This way we generated a 2D coordination polymer of the desired composition, [Na2(thf)1.5][(Me2PhPAg)(PhSi)3S6] (6). UV‐visible spectra of 6 indicated a bandgap of 3.89 eV, thus blue‐shifted in regards to B and C.

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Synthesis and Characterization of a New Binucleating Tetraphosphine Ligand Based on 1,2-Phenylene Chelates and the Structures of Dinickel Tetrachloride Complexes of the Ligand

Cited by 5 publications

References 16 publications

Phosphine Oxides from a Medicinal Chemist’s Perspective: Physicochemical and in Vitro Parameters Relevant for Drug Discovery

Phosphine Oxides from a Medicinal Chemist’s Perspective: Physicochemical and in Vitro Parameters Relevant for Drug Discovery

Highly active cationic cobalt(II) hydroformylation catalysts

Dimers and 2D Networks of Adamantane‐Related Ternary Organosilicon Coinage Metal Sulfide Clusters

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