Fluorocarbonyl Trifluoromethanesulfonate, FC(O)OSO2CF3: Structure and Conformational Properties in the Gaseous and Condensed Phases
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- 作者：Carlos O. Della Vé ; dova ; Anthony J. Downs ; Vladimir P. Novikov ; Heinz Oberhammer ; Simon Parsons ; Rosana M. Romano ; and Alex Zawadski
- 刊名：Inorganic Chemistry
- 出版年：2004
- 出版时间：June 28, 2004
- 年：2004
- 卷：43
- 期：13
- 页码：4064 - 4071
- 全文大小：153K
- 年卷期：v.43,no.13(June 28, 2004)
- ISSN：1520-510X
文摘
Pure fluorocarbonyl trifluoromethanesulfonate, FC(O)OSO2CF3, is prepared in about 70% yield by the ambient-temperature reaction between FC(O)SCl and AgCF3SO3. The geometric structure and conformational properties ofthe gaseous molecule have been studied by gas electron diffraction (GED), vibrational spectroscopy [IR(gas),IR(matrix), and Raman(liquid)] and quantum chemical calculations (HF, MP2, and B3LYP with 6-311G* basis sets);in addition, the solid-state structure has been determined by X-ray crystallography. FC(O)OSO2CF3 exists in thegas phase as a mixture of trans [FC(O) group trans with respect to the CF3 group] and gauche conformers withthe trans form prevailing [67(8)% from GED and 59(5)% from IR(matrix) measurements]. In both conformers theC=O bond of the FC(O) group is oriented synperiplanar with respect to the S-O single bond. The experimentalfree energy difference between the two forms, 
G
= 0.49(13) kcal mol-1 (GED) and 0.22(12) kcal mol-1 (IR),is slightly smaller than the calculated value (0.74-0.94 kcal mol-1). The crystalline solid at 150 K [monoclinic,P21/c, a = 10.983(1) Å, b = 6.4613(6) Å, c = 8.8508(8) Å, 
= 104.786(2)] consists exclusively of the transconformer.
G = 0.49(13) kcal mol-1 (GED) and 0.22(12) kcal mol-1 (IR),is slightly smaller than the calculated value (0.74-0.94 kcal mol-1). The crystalline solid at 150 K [monoclinic,P21/c, a = 10.983(1) Å, b = 6.4613(6) Å, c = 8.8508(8) Å, = 104.786(2)] consists exclusively of the transconformer.