Synthesis and Characterization of the Silylated Hexaphenyl Carbodiphosphorane [Me3SiC(PPh3)2][CF3SO3] |
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Authors: | Istemi Kuzu Nis‐Julian H. Kneusels Mona Bauer Bernhard Neumüller Ralf Tonner |
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Affiliation: | Philipps‐Universit?t Marburg, Fachbereich Chemie, Hans‐Meerwein‐Stra?e, 35032 Marburg, Germany |
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Abstract: | The addition of trimethylsilyl trifluoromethanesulfonate TMS‐OTf (CF3SO3 = OTf, triflate) to hexaphenyl carbodiphosphorane PPh3=C=PPh3 ( 1 ) in toluene yields the silylated carbodiphosphorane [Me3SiC(PPh3)2][OTf] ( 2 ). Compound 2 represents the first silylated carbodiphosphorane characterized in solution and in the solid state. 2 is an air‐sensitive compound but stable in solution and in the solid state in an inert atmosphere as shown by heteronuclear NMR experiments and also by X‐ray diffraction analysis. Compound 2 crystallizes in the monoclinic space group P21/n with the cell dimensions a = 1161.7(1), b = 1714.4(1), c = 1903.3(1) pm; β = 102.74(1)° and Z = 4. Structure, frontier orbitals, and dissociation energies for 2 were determined by density functional theory‐based computations highlighting the character of 2 as a Lewis acid adduct of a carbon(0) compound. |
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Keywords: | Carbodiphosphoranes NMR spectroscopy Silicon Density functional calculations |
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