Mechanistic Insights into the Appel Reaction Mediated by a Poly-Phosphamide Material as a Heterogeneous Catalyst

Kumari, Nidhi; Mahata, Anup; Chakraborty, Biswarup

doi:10.1021/acs.inorgchem.3c02989

Inorg. Chem.

2023

DOI: 10.1021/acs.inorgchem.3c02989

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Mechanistic Insights into the Appel Reaction Mediated by a Poly-Phosphamide Material as a Heterogeneous Catalyst

Nidhi Kumari,

Anup Mahata,

Biswarup Chakraborty

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2024

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Cited by 2 publications

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Catalytic Appel Reaction Accessing the Mesoporous Substructure of a Robust and Heterogeneous Polyphosphamide

Mahata,

Kumari,

Chakraborty

2024

ChemCatChem

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While phosphamides are well flame retardants, herein a mesoporous polyphosphamide (p‐PPA) with an accessible average pore diameter of <10 nm and a surface area of 1.773 m2/g has been synthesized via condensation of 1,3‐diamino benzene (DAB) and phenyl phosphinic dichloride (PPDC). 31P, 13C CP‐MAS NMR, Raman spectra, and X‐ray photon spectroscopic (XPS) characterizations confirm the presence of ‐{PV(O)‐NH}‐ in the repeating unit of the p‐PPA that is further used as a catalytic mediator to perform the Appel reaction i.e., conversion of alcohols to halides with a broad substrate scope and high TON (561). The heterogeneity of p‐PPA allows easy recovery of organic halides and recycling of the catalyst many times. Mesoporous p‐PPA have further given a scope to perform shape‐selective conversion of primary alcohols with linear alkyl chain (1‐dodecanol) while low conversions for the bulky secondary (cyclo‐hexanol) and tertiary alcohol (tert‐butanol) are observed. Perhaps, the phosphamide units present inside the porous sites are non‐preferable site for bulkier alcohols, as evident from the competitive experiments. A comparatively less catalytic conversion obtained with an analogous non‐porous n‐PPA, made of tris(2‐aminoethyl)amine (TREN) linker, highlights the role of porosity in p‐PPA to enhances the accessibility of numerous ‐{PV(O)‐NH}‐ reactive units to increase the TON.

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Catalytic Appel Reaction Accessing the Mesoporous Substructure of a Robust and Heterogeneous Polyphosphamide

Mahata,

Kumari,

Chakraborty

2024

ChemCatChem

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Moderation of the Electronic Structure of Phosphamides to Execute the Catalytic Appel Reaction Bypassing Phosphine

Kumari,

Jagadeesh,

Galav

et al. 2024

J. Org. Chem.

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A set of structurally analogous, albeit electronically distinct, phosphamides (1aa-10aa) is prepared, and the effect of the electronic amendment due to p-substitution has been tested for the conversion of alcohols to halides via the Appel reaction. The −OMe-substituted diphosphamide (8aa) remains the most active, providing ∼96% conversion of alcohols to halides with a TON of 11 in moderate reaction conditions with a large substrate scope. Halide formation follows a pseudo-first-order rate with a constant rate (k obs ) of 7.13 × 10 −5 s −1 . Temp-dependent kinetics and Eyring analyses reveal the activation parameters ΔH ‡ of 28.95 (±1.6) kcal mol −1 , ΔS ‡ of −70.02 (±0.4) cal K −1 mol −1 , and ΔG ‡ 298 of 49.81 (±1.2) kcal mol −1 . The deuterium labeling study highlights the O−H dissociation of the alcohol as the rate-determining step, while the Hammett analysis with p-substituted benzyl alcohols indicates a positive charge accumulation at the phosphorus center during the Appel reaction. The HOMO−LUMO energy and NPA analyses show that p−OMe substitutions in 8aa make the "P�O" bond more ionic and corresponding aminophosphine is nucleophilic, which are favorable for the Appel reaction. In situ detection of the Appel salt, [R 3 PX]CX 3 and alkoxy phosphonium cation [R 3 POR]X, validates the reaction pathway mediated by the phosphamides.

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Mechanistic Insights into the Appel Reaction Mediated by a Poly-Phosphamide Material as a Heterogeneous Catalyst

Cited by 2 publications

References 37 publications

Catalytic Appel Reaction Accessing the Mesoporous Substructure of a Robust and Heterogeneous Polyphosphamide

Catalytic Appel Reaction Accessing the Mesoporous Substructure of a Robust and Heterogeneous Polyphosphamide

Moderation of the Electronic Structure of Phosphamides to Execute the Catalytic Appel Reaction Bypassing Phosphine

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