Fused Tricyclic Phosphiranes—Analysis of Phosphorus Chemical Shieldings

Authors

  • Erik P. A. Couzijn,

    1. Department of Organic Chemistry, Faculty of Sciences, Vrije Universiteit, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands, Fax: (+31) 20-598-7488
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  • Andreas W. Ehlers Dr.,

    1. Department of Organic Chemistry, Faculty of Sciences, Vrije Universiteit, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands, Fax: (+31) 20-598-7488
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  • J. Chris Slootweg Dr.,

    1. Department of Organic Chemistry, Faculty of Sciences, Vrije Universiteit, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands, Fax: (+31) 20-598-7488
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  • Marius Schakel Dr.,

    1. Department of Organic Chemistry, Faculty of Sciences, Vrije Universiteit, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands, Fax: (+31) 20-598-7488
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  • Steffen Krill Dr.,

    1. Formerly associated with the Department of Chemistry, University of Alabama at Birmingham, Birmingham, AL 35294, USA
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  • Martin Lutz Dr.,

    1. Crystal and Structural Chemistry, Bijvoet Center for Biomolecular Research, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands
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  • Anthony L. Spek Prof. Dr.,

    1. Crystal and Structural Chemistry, Bijvoet Center for Biomolecular Research, Utrecht University, Padualaan 8, 3584 CH Utrecht, The Netherlands
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  • Koop Lammertsma Prof. Dr.

    1. Department of Organic Chemistry, Faculty of Sciences, Vrije Universiteit, De Boelelaan 1083, 1081 HV, Amsterdam, The Netherlands, Fax: (+31) 20-598-7488
    2. Formerly associated with the Department of Chemistry, University of Alabama at Birmingham, Birmingham, AL 35294, USA
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Abstract

1,2-Addition of transient W(CO)5-complexed phosphinidenes exo to hexamethyl Dewar benzene affords the novel 3-phosphatricyclo[3.2.0.02,4]hept-6-ene complexes. The fused tricyclic phosphiranes are obtained as both the Z and the thermally less stable E isomers, the 31P 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 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.

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