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A Terphenyl Supported Dioxophosphorane Dimer: the Light Congener of Lawesson's and Woollins’ Reagents
Author(s) -
English Laura E.,
Pajak Aleksandra,
McMullin Claire L.,
Lowe John P.,
Mahon Mary F.,
Liptrot David J.
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202200376
Subject(s) - terphenyl , isostructural , dimer , yield (engineering) , pyridine , chemistry , ring (chemistry) , reagent , nuclear magnetic resonance spectroscopy , spectroscopy , thermal decomposition , medicinal chemistry , crystallography , stereochemistry , materials science , organic chemistry , crystal structure , physics , quantum mechanics , metallurgy
Thermolysis of a 1,3‐dioxa‐2‐phospholane supported by the terphenyl ligand Ar iPr4 (Ar iPr4 =[C 6 H 3 ‐2,6‐(C 6 H 3 ‐2,6‐iPr 2 )]) at 150 °C gives [Ar iPr4 PO 2 ] 2 via loss of ethene. [Ar iPr4 PO 2 ] 2 was characterised by X‐ray crystallography and NMR spectroscopy; it contains a 4‐membered P−O−P−O ring and is the isostructural oxygen analogue of Lawesson's and Woollins’ reagents. The dimeric structure of [Ar iPr4 PO 2 ] 2 was found to persist in solution through VT NMR spectroscopy and DOSY, supported by DFT calculations. The addition of DMAP to the 1,3‐dioxa‐2‐phospholane facilitates the loss of ethene to give Ar iPr4 (DMAP)PO 2 after days at room temperature, with this product also characterised by X‐ray crystallography and NMR spectroscopy. Replacement of the DMAP with pyridine induces ethene loss from the 1,3‐dioxa‐2‐phospholane to provide gram‐scale samples of [Ar iPr4 PO 2 ] 2 in 75 % yield in 2 days at only 100 °C.