Ambiphilic phosphorus compounds: synthesis, structure and application in activation of small molecules

The scientific goal of the project is the synthesis of ambiphilic phosphorus compounds: phosphinophosphoranes RR’P-PL2 and geminal phosphinophosphoranes: RR’P-O-L2 and RR’P-CH2-L2 (R, R’ = tBu, Ph, Cy, iPr and L = bidentate chelating ligand: catechol, pinacol, N-methylurea, oxalate, perfluoropinacol or perfluorocatechol) and their application in activation of small molecules. The latter ones may be considered as intrarmolecular frustrated Lewis Pair in which reactive phosphorus center acts as both a Lewis basic (RR’P- ) and the Lewis acidic (-PL2) component, which is an unprecedented concept in the FLP chemistry. Our aim is to create systems that because of steric and electronic features will be able to mimic transition metals. We assume that rational P-based systems design featuring the presence of both, Lewis basic (RR’P) and Lewis acidic (PL2) sites together with an understanding of the crucial steps in the reaction mechanism may facilitate the activation of small molecules by these pairs. It may lead to unique and sought-after reactivity where a main-group element is capable of outperforming its transition metal counterparts. Resulting products will be fully characterized and their reactivity will be tested in the reactions with H2, CO2, SO2, N2O, CS2 as well as PhNCO, PhNCS, PhNSO, RR’CO, and RCHO.

Details

Financial Program Name:

PRELUDIUM

Organization:

Narodowe Centrum Nauki (NCN) (National Science Centre)

Agreement:

UMO-2019/35/N/ST4/03168 z dnia 2020-06-25

Realisation period:

2020-06-25 - 2022-06-24

Project manager:

mgr inż. Natalia Szynkiewicz

Team members:

Research supervisor dr hab. inż. Rafał Grubba

Realised in:

Department of Inorganic Chemistry

Project's value:

139 200.00 PLN

Request type:

National Research Programmes

Domestic:

Domestic project

Verified by:

Gdańsk University of Technology

Papers associated with that project

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total: 2

Year 2022

Exploring the Reactivity of Unsymmetrical Diphosphanes toward Heterocumulenes: Access to Phosphanyl and Phosphoryl Derivatives of Amides, Imines, and Iminoamides
Publication
- INORGANIC CHEMISTRY - Year 2022
We present a comprehensive study on the diphosphanation of iso(thio)cyanates by unsymmetrical diphosphanes. The reactions involving unsymmetrical diphosphanes and phenyl isocyanate or phenyl thioisocyanate gave rise to phosphanyl, phosphoryl, and thiophosphoryl derivatives of amides, imines, and iminoamides. The structures of the diphosphanation products were confirmed through NMR spectroscopy, IR spectroscopy, and single-crystal...

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Phosphinophosphoranes: Mixed-Valent Phosphorus Compounds with Ambiphilic Properties
Publication
- INORGANIC CHEMISTRY - Year 2022
Herein, we present a simple synthesis of mixed-valent phosphinophosphoranes bearing three- and five-coordinate phosphorus centers. Compounds with phosphorus–phosphorus bonds were synthesized via a reaction of lithium phosphides RR′PLi with cat2PCl (cat = catecholate), whereas derivatives with methylene-linked phosphorus centers were obtained via a reaction of phosphanylmethanides RR′CH2Li with cat2PCl. The presence of accessible...

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