The Coordination and Catalytic Chemistry of Phosphanylferrocene Chalcogenides

Štěpnička, Petr; Horký, Filip

doi:10.1002/ejic.202200276

Cited by 4 publications

(1 citation statement)

References 151 publications

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“…Next, the family of stibine and stiborane derivatives was expanded by compounds featuring heavier P-chalcogenides 30 to establish the possible influence of the chalcogenide donor atom on the E → Sb interaction ( Scheme 5 ). The oxidation changes not only the possible donor atom and the donor···Sb distance but also the electron density distribution in the system.…”

Section: Resultsmentioning

confidence: 99%

Synthesis, Structure, Reactivity, and Intramolecular Donor–Acceptor Interactions in a Phosphinoferrocene Stibine and Its Corresponding Phosphine Chalcogenides and Stiboranes

Schulz,

Antala,

Rezazgui

et al. 2023

Inorg. Chem.

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Ferrocene-based phosphines equipped with additional functional groups are versatile ligands for coordination chemistry and catalysis. This contribution describes a new compound of this type, combining phosphine and stibine groups at the ferrocene backbone, viz. 1-(diphenylphosphino)-1′-(diphenylstibino)ferrocene (1). Phosphinostibine 1 and the corresponding P-chalcogenide derivatives Ph2P(E)fcSbPh2 (1E, fc = ferrocene-1,1′-diyl, E = O, S, Se) were synthesized and further converted to the corresponding stiboranes Ph2P(E)fcSb(O2C6Cl4)Ph2 (6 and 6E) by oxidation with o-chloranil. All compounds were characterized by spectroscopic methods, X-ray diffraction analysis, cyclic voltammetry, and theoretical methods. Both NMR spectroscopy and DFT calculations confirmed the presence of P → Sb and PO → Sb donor–acceptor interactions in 6 and 6O, triggered by the oxidation of the stibine moiety into Lewis acidic stiborane. The corresponding interactions in 6S and 6Se were of the same type but significantly weaker. A coordination study with AuCl as the model metal fragment revealed that the phosphine group acts as the “primary” coordination site, in line with its higher basicity. The obtained Au(I) complexes were applied as catalysts in the Au-catalyzed cyclization of N-propargylbenzamide and in the oxidative [2 + 2 + 1] cyclization of ethynylbenzene with acetonitrile and pyridine N-oxides. The catalytic results showed that the stibine complexes had worse catalytic performance than their phosphine counterparts, most likely due to the formation of weaker coordination bonds and hence poorer stabilization of the active metal species. Nevertheless, the stibine moiety could be used to fine-tune the properties of the ligated metal center by changing the oxidation state or substituents at the “remote” Sb atom.

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Section: Resultsmentioning

confidence: 99%

Synthesis, Structure, Reactivity, and Intramolecular Donor–Acceptor Interactions in a Phosphinoferrocene Stibine and Its Corresponding Phosphine Chalcogenides and Stiboranes

Schulz,

Antala,

Rezazgui

et al. 2023

Inorg. Chem.

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Application of Primary Phosphine Oxides in Domino‐Phospha‐Aldol Reactions of Diketones

Horký,

Bruhn,

Kargin

et al. 2024

Adv Synth Catal

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An approach for the preparation and stabilization of primary phosphine oxides is presented complementing previous methods of in situ generation. Specifically, RP(O)H2 where R = benzyl (Bn), cyclohexyl (Cy), 2‐naphthyl (2‐Naph), phenyl (Ph), tert‐butyl (t‐Bu) was prepared by controlled oxidation of the corresponding primary phosphine in presence of ferrocene as stabilizing reagent. The primary phosphine oxides were characterized using NMR and MS and studied in twofold hydro phosphorylation of diketones. The domino‐phospha‐aldol reaction catalysed with 5 mol% of sodium methoxide yielded five‐, six‐ and seven‐membered heterocyclic tertiary phosphine oxides with a high degree of stereoselectivity, as confirmed by single X‐ray diffraction.

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A General Strategy for Increasing the Air Stability of Phosphines Including Primary Phosphines

Horký,

Franz,

Bruhn

et al. 2023

Chemistry A European J

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Given recent reports of structurally diverse air‐stable primary phosphines lacking kinetic stabilization, the stability against oxidation was difficult to rationalize and attributed to the specific electronic nature of the phosphine group. This contribution shows the synthesis of a series of air‐stable primary phosphines Fc(CH2)nPH2, where n = 0,1,2,3; and Fc = ferrocenyl, and their corresponding isolable primary phosphine oxides. It was demonstrated that the ferrocene moiety exerts an antioxidant effect on the primary phosphine group, which is intermolecular, solvent dependent and increases with the electron density on the ferrocene moiety. Furthermore, we demonstrated that the presence of ferrocene in solution also inhibits the oxidation of other secondary and tertiary phosphines in air. The collected information suggests that quenching of singlet oxygen is the actual reason for the antioxidant effect which was experimentally confirmed using other established singlet oxygen quenchers as well, demonstrating a key role of singlet oxygen in the aerobic oxidation of phosphines.

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The Coordination and Catalytic Chemistry of Phosphanylferrocene Chalcogenides

Cited by 4 publications

References 151 publications

Synthesis, Structure, Reactivity, and Intramolecular Donor–Acceptor Interactions in a Phosphinoferrocene Stibine and Its Corresponding Phosphine Chalcogenides and Stiboranes

Synthesis, Structure, Reactivity, and Intramolecular Donor–Acceptor Interactions in a Phosphinoferrocene Stibine and Its Corresponding Phosphine Chalcogenides and Stiboranes

Application of Primary Phosphine Oxides in Domino‐Phospha‐Aldol Reactions of Diketones

A General Strategy for Increasing the Air Stability of Phosphines Including Primary Phosphines

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