Abstract
The gas-phase structures of ethynyl- and vinyl sulfur pentafluoride were determined by joint analyses of electron diffraction and microwave spectroscopic data. The following skeletal geometric parameters ( r z values with 3σ uncertainties) were obtained. SF 5CCH: (SF) mean = 1.574 (1) Å, ΔSF=(SF eSF a)=0.018 (14) Å, SC=1.736 (6) Å, CC=1.200 (7) Å, F eSF a=88.9 (2)°; SF 5CHCH 2: (SF) mean 1.581 (1) Å, ΔSF=0.020 (16) Å, SC=1.787 (9) Å, CC=1.337 (17) Å, F eSF a=88.4 (3)° SCC=124.5 (15)°. In both compounds the equatorial SF bonds are longer than the axial ones, in accordance with the predicted “cis influence” in octahedral main group element compounds. The actual values for the bond length differences ΔSF, however, are poorly determined. The variation of the (SF) mean bond lengths between the ethynyl and vinyl derivatives can be rationalized by the different group electronegativities of these two substituents. The variation of the SC bond lengths reflects the different covalent radii of sp and sp 2 hybridized carbon atoms.
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