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The molecular structures of the two trifluoromethyl phosphoranes (CF 3 ) 2 PCl 3  and (CF 3 ) 3 PCl 2  have been determined by electron diffraction of gases. The structure of (CF 3 ) 2 PCl 3  was found to be a regular trigonal bipyramid with both CF 3  groups in axial positions (D 3h  symmetry) and the fluorine atoms staggered to the equatorial chlorine atoms. The following geometric parameters (r a -values) were obtained: r(C-F) = 1.331(2) Å, r(P-C) = 1.950(II) Å, r(P-Cl) = 2.036(2) Å and ⦓ FCF = 108.3°(0.4). (CF 3 ) 3 PCl 2  possesses the structure of a distorted trigonal bipyramid with two CF 3  groups in axial and one in equatorial position. Again the fluorine atoms of the axial CF 3  groups are staggered to the equatorial atoms. The r a -values for the geometric parameters are: r(C-F)= 1.329(2) Å, r(P-C) eq = 1.938(31) Å, r(P-C) ax  = 1.946(14) Å, r(P-Cl) = 2.053(6) Å, ⦓ FCF = 108.5°(0.3), ⦓ ClPCl = 133.0°(1.7) and ⦓ C ax PC eq  = 95.5°(1.9). The average P-C bond length was found to be r(P-C) av  = 1.943(5) A. The results for the mean square amplitudes are given in the article. It was shown that in both molecules the torsional amplitudes of the CF 3  groups around the P-C bond directions are small, indicating high potential barriers to internal rotation.

zeitschrift für naturforschung b

Molekülstrukturen von Phosphorverbindungen, IV / Molecular Structures of Phosphorus Compounds, IV: Bis(trifluormethyl)trichlorphosphoran (CF 3 ) 2 PCl 3  und Tris(trifluormethyl)dichlorphosphoran (CF 3 ) 3 PCl 2  / Bis (trifluoromethyl)trichlorophosphorane (CF 3 ) 2 PCl 3  and Tris (trifluoromethyl)dichlorophosphorane (CF 3 ) 3 PCl 2