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2‐(Trimethylsilyl)‐λ 3 ‐Phosphinine: Synthesis, Coordination Chemistry, and Reactivity
Author(s) -
Habicht Marija H.,
Wossidlo Friedrich,
Bens Tobias,
Pidko Evgeny A.,
Müller Christian
Publication year - 2018
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.201704539
Subject(s) - trimethylsilyl , chemistry , cycloaddition , pericyclic reaction , regioselectivity , reactivity (psychology) , ligand (biochemistry) , silylation , allene , medicinal chemistry , organic chemistry , catalysis , medicine , biochemistry , alternative medicine , receptor , pathology
The [4+2] cycloaddition reaction between 2‐pyrone and Me 3 Si−C≡P gives the corresponding 2‐(trimethylsilyl)‐λ 3 ‐phosphinine in good yields as a rather air and moisture stable, colorless oil. Insight into the regioselectivity of the pericyclic reaction was obtained with the help of deuterium‐labeling experiments. The silyl‐phosphinine acts as a ligand for the preparation of a Cu(I) and the first crystallographically characterized phosphinine‐Ag(I) complex. The title compound was further used as a starting material for an alternative preparation of the parent phosphinine C 5 H 5 P by means of protodesilylation with HCl. C 5 H 5 P reacts with CuBr⋅S(CH 3 ) 2 to give an infinite Cu(I)Br coordination polymer. DFT calculations shed light on the influence of the ‐Si(CH 3 ) 3 group on the electronic properties of the aromatic phosphorus heterocycle.