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Trimerization and cyclization of reactive P-functionalities confined within OCO pincers.

ABSTRACT: In order to stabilize a 10-P-3 species with C _2v symmetry and two lone pairs on the central phosphorus atom, a specialized ligand is required. Using an NCN pincer, previous efforts to enforce this planarized geometry at P resulted in the formation of a C _s-symmetric, 10π-electron benzazaphosphole that existed as a dynamic "bell-clapper" in solution. Here, OCO pincers 1 and 2 were synthesized, operating under the hypothesis that the more electron-withdrawing oxygen donors would better stabilize the 3-center, 4-electron O-P-O bond of the 10-P-3 target and the sp³-hybridized benzylic carbon atoms would prevent the formation of aromatic P-heterocycles. However, subjecting 1 to a metalation/phosphination/reduction sequence afforded cyclotriphosphane 3, resulting from trimerization of the P(i) center unbound by its oxygen donors. Pincer 2 featuring four benzylic CF₃ groups was expected to strengthen the O-P-O bond of the target, but after metal-halogen exchange and quenching with PCl₃, unexpected cyclization with loss of CH₃Cl was observed to give monochlorinated 5. Treatment of 5 with (p-CH₃)C₆H₄MgBr generated crystalline P-(p-Tol) derivative 6, which was characterized by NMR spectroscopy, elemental analysis, and X-ray crystallography. The complex ¹⁹F NMR spectra of 5 and 6 observed experimentally, were reproduced by simulations with MestreNova.

SUBMITTER: Chinen BL

PROVIDER: S-EPMC9038090 | biostudies-literature | 2021 Aug

REPOSITORIES: biostudies-literature

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Trimerization and cyclization of reactive P-functionalities confined within OCO pincers.

Chinen Beatrice L BL Hyvl Jakub J Brayton Daniel F DF Riek Matthew M MM Yoshida Wesley Y WY Chapp Timothy W TW Rheingold Arnold L AL Cain Matthew F MF

RSC advances 20210825 46

In order to stabilize a 10-P-3 species with C 2v symmetry and two lone pairs on the central phosphorus atom, a specialized ligand is required. Using an NCN pincer, previous efforts to enforce this planarized geometry at P resulted in the formation of a C s-symmetric, 10π-electron benzazaphosphole that existed as a dynamic "bell-clapper" in solution. Here, OCO pincers 1 and 2 were synthesized, operating under the hypothesis that the more electron-withdrawing ox ...[more]

PMID: 35478534

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Project description:Sulfur-containing groups preorganized on macrocyclic scaffolds are well suited for liquid-phase complexation of soft metal ions; however, their binding potential was not extensively studied at the air-water interface, and the effect of thioether topology on metal ion binding mechanisms under various conditions was not considered. Herein, we report the interface receptor characteristics of topologically varied thiacalixarene thioethers (linear bis-(methylthio)ethoxy derivative L2, O2S2-thiacrown-ether L3, and O2S2-bridged thiacalixtube L4). The study was conducted in bulk liquid phase and Langmuir monolayers. For all compounds, the highest liquid-phase extraction selectivity was revealed for Ag+ and Hg2+ ions vs. other soft metal ions. In thioether L2 and thiacalixtube L4, metal ion binding was evidenced by a blue shift of the band at 303 nm (for Ag+ species) and the appearance of ligand-to-metal charge transfer bands at 330-340 nm (for Hg2+ species). Theoretical calculations for thioether L2 and its Ag and Hg complexes are consistent with experimental data of UV/Vis, nuclear magnetic resonance (NMR) spectroscopy, and single-crystal X-ray diffractometry of Ag-thioether L2 complexes and Hg-thiacalixtube L4 complex for the case of coordination around the metal center involving two alkyl sulfide groups (Hg2+) or sulfur atoms on the lower rim and bridging unit (Ag+). In thiacrown L3, Ag and Hg binding by alkyl sulfide groups was suggested from changes in NMR spectra upon the addition of corresponding salts. In spite of the low ability of the thioethers to form stable Langmuir monolayers on deionized water, one might argue that the monolayers significantly expand in the presence of Hg salts in the water subphase. Hg2+ ion uptake by the Langmuir-Blodgett (LB) films of ligand L3 was proved by X-ray photoelectron spectroscopy (XPS). Together, these results demonstrate the potential of sulfide groups on the calixarene platform as receptor unit towards Hg2+ ions, which could be useful in the development of Hg2+-selective water purification systems or thin-film sensor devices.

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Trimerization and cyclization of reactive P-functionalities confined within OCO pincers.

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Trimerization and cyclization of reactive P-functionalities confined within OCO pincers.

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