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Fused Tricyclic Phosphiranes—Analysis of Phosphorus Chemical Shieldings
Author(s) -
Couzijn Erik P. A.,
Ehlers Andreas W.,
Slootweg J. Chris,
Schakel Marius,
Krill Steffen,
Lutz Martin,
Spek Anthony L.,
Lammertsma Koop
Publication year - 2008
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.200700958
Subject(s) - tricyclic , adduct , chemistry , double bond , benzene , chemical shift , phosphorus , bond length , medicinal chemistry , stereochemistry , organic chemistry , molecule
1,2‐Addition of transient W(CO) 5 ‐complexed phosphinidenes exo to hexamethyl Dewar benzene affords the novel 3‐phosphatricyclo[3.2.0.0 2,4 ]hept‐6‐ene complexes. The fused tricyclic phosphiranes are obtained as both the Z and the thermally less stable E isomers, the 31 P NMR chemical shifts of which differ by about 60 ppm. A computational investigation shows that the phosphorus pyramidalization and the presence of the γ double bond are responsible for this effect. The semiquantitative results contribute to a more systematic understanding of the structural influences on 31 P chemical shieldings. The congested double bond of the Z isomer can be epoxidized with m ‐chloroperbenzoic acid (MCPBA) to afford a fused tetracyclic P,O bis‐adduct.