Fused tricyclic phosphiranes - Analysis of phosphorus chemical shielding

Erik P.A. Couzijn; Andreas W. Ehlers; J. Chris Slootweg; Marius Schakel; Steffen Krill; Martin Lutz; Anthony L. Spek; Koop Lammertsma

doi:10.1002/chem.200700958

Fused tricyclic phosphiranes - Analysis of phosphorus chemical shielding

Erik P.A. Couzijn, Andreas W. Ehlers, J. Chris Slootweg, Marius Schakel, Steffen Krill, Martin Lutz, Anthony L. Spek, Koop Lammertsma

Research output: Contribution to journal › Article › peer-review

14 Citations (Scopus)

Abstract

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 ³¹PNMR 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 ³¹P 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.

Original language	English
Pages (from-to)	1499-1507
Number of pages	9
Journal	Chemistry - A European Journal
Volume	14
Issue number	5
DOIs	https://doi.org/10.1002/chem.200700958
Publication status	Published - 8 Feb 2008
Externally published	Yes

Keywords

Density functional calculations
Fused-ring systems
NMR spectroscopy
Phosphorus heterocycles
Ring strain

ASJC Scopus subject areas

Catalysis
General Chemistry
Organic Chemistry

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10.1002/chem.200700958

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title = "Fused tricyclic phosphiranes - Analysis of phosphorus chemical shielding",

abstract = "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 31PNMR 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 31P 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.",

keywords = "Density functional calculations, Fused-ring systems, NMR spectroscopy, Phosphorus heterocycles, Ring strain",

author = "Couzijn, {Erik P.A.} and Ehlers, {Andreas W.} and Slootweg, {J. Chris} and Marius Schakel and Steffen Krill and Martin Lutz and Spek, {Anthony L.} and Koop Lammertsma",

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doi = "10.1002/chem.200700958",

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T1 - Fused tricyclic phosphiranes - Analysis of phosphorus chemical shielding

AU - Couzijn, Erik P.A.

AU - Ehlers, Andreas W.

AU - Slootweg, J. Chris

AU - Schakel, Marius

AU - Krill, Steffen

AU - Lutz, Martin

AU - Spek, Anthony L.

AU - Lammertsma, Koop

PY - 2008/2/8

Y1 - 2008/2/8

N2 - 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 31PNMR 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 31P 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.

AB - 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 31PNMR 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 31P 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.

KW - Density functional calculations

KW - Fused-ring systems

KW - NMR spectroscopy

KW - Phosphorus heterocycles

KW - Ring strain

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DO - 10.1002/chem.200700958

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SN - 0947-6539

VL - 14

SP - 1499

EP - 1507

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 5

ER -

Fused tricyclic phosphiranes - Analysis of phosphorus chemical shielding

Abstract

Keywords

ASJC Scopus subject areas

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