Structure Determinations of the Sulfonic Acid Monofluoromethylesters FSO2OCH2F and CF3SO2OCH2F in the Solid and Gaseous Phases

我们建议在固相和气相中研究磺酸单氟甲基酯FSO_2 OCH_2F和CF_3SO_2 OCH_2F的结构。这些化合物是小的磺酸酯，是一类重要化合物的简单代表，因此具有根本意义。我们期望获得对简单的氟甲基磺酸盐的结构、它们在这类化合物中的反应性和化学性质的详细了解。从F到CF 3的吸电子取代基的变化以及结构和构象行为变化的比较研究将使人们对取代基的成键性质和电子影响有新的认识。这将有助于指导对新的和迄今未知的氟甲基化试剂的进一步研究，并解释甲基和氟甲基化试剂之间反应行为的差异。这些潜在的强氟甲基化剂的结构和稳定性性质之间的可能关系是本研究的另一个目标。我们计划通过对这些液体物质应用合适的结晶技术来阐明磺酸单氟甲基酯FSO 2 OCH 2F和CF 3SO 2 OCH 2F的晶体结构，以获得用于X射线衍射的晶体，从而获得可解析的固态结构。如果可能的话，我们还计划通过高角X射线衍射确定电子密度拓扑结构，以详细分析化合物内的电子效应。利用X射线晶体学的结果，我们希望得到更准确的计算数据的分子间和分子内的相互作用的系统。该项目的核心部分是通过电子衍射实验和衍射数据分析来探索这些化合物的实验气相结构-必要时对分子进行复杂的动态描述。样品制备和纯化将在慕尼黑进行，样品转移至比勒费尔德，并在比勒费尔德的核心设施GED@BI（气体电子衍射和小分子结构中心）进行气体和固体结构研究。这些实验研究将伴随着高水平的量子化学方法。

We propose to study the structures of the sulfonic acid monofluoromethylesters FSO2OCH2F and CF3SO2OCH2F in the solid and gaseous phases. These compounds are small sulfonic acid esters and simple representatives of an important class of compounds and thus of fundamental interest. We expect to get achieve a detailed under¬standing of the structures of simple fluoromethyl sulfonates, their reactivity and chemistry within this class of compounds. The variation of electron-withdrawing substituents from F to CF3 and the comparative study of the changes in structure and conformational behaviour will allow new insights into the nature of bonding and electronic influences of substituents. This should help to guide further research into new and hitherto unknown fluoromethylating agents and to explain the difference in reaction behaviour between methyl and fluoromethylating agents. A possible relation between structure and stability properties of these potentially strong fluoro¬methylating agents is a further target of this research. We plan to elucidate the crystal structures of the sulfonic acid monofluoromethylesters FSO2OCH2F and CF3SO2OCH2F by applying suitable crystallization techniques to these liquid substances in order to gain crystals for X-ray diffraction that lead to resolvable structures of the solid state. If possible, we also plan to determine the electron density topologies by high angle X-ray diffraction for a detailed analysis of the electronic effects within the compounds. By making use of the X-ray crystallographic results we hope to receive more accurate computational data of their inter- and intramolecular interactions in the system. Central part of the project is to explore the experimental gas phase structures of these compounds by electron diffraction experiments and analysis of the diffraction data – if necessary with sophisticated dynamic descriptions of the molecules. The sample preparation and purification will be performed in Munich, the samples transferred to Bielefeld and structural studies in gas and solid performed in the core facility GED@BI (Centre of Gas Electron Diffraction and Small Molecule Structures) in Bielefeld. These experimental studies will be accompanied by high level quantum-chemical methods.