Halogenated materials from novel reactive halogenating ionic liquids

本项目旨在研究新型反应性卤化离子液体的合成、表征及其在新型卤化材料合成中的应用。卤化试剂由多卤阴离子组成，通式为[F(XF)n]-（其中X = Cl, Br， I, n = 1-4）。有了合适的阳离子，这些卤化物间盐本身就代表离子液体，或者它们与离子液体一起用作液化剂。由于气体的高溶解度和与溶质的弱相互作用，离子液体是合成和应用此类多卤单阴离子的理想介质。此外，它们可以被设计成对Cl2、ClF甚至单质氟等强氧化剂具有很强的抵抗力。在合适的离子液体中，裸露的F-与卤素单氟化物XF反应制备多卤素单阴离子。另外，将研究多卤化物盐（[Cat]+[X(X2)n]-, X = Cl, Br， I和n = 1-4）与F2/N2混合物的反应。这种溶解在离子液体中的卤化物盐应该是通用的卤化试剂，它比气态强氧化剂ClF或F2更安全，更容易处理。由于它们的高热容量，它们是缓和通常相当放热的卤化反应的良好介质。对于新材料的合成，我们希望使用这些反应性离子液体，特别是在i) 1,1加成和1,2加成，ii)卤素交换反应和iii) -CN到-CF3的转化。特别需要的弱配位近硼酸盐和近碳酸盐阴离子，如[B12X12]2-， [CB11X12]- （X = F, Cl, Br， I）和相应的三氟甲基取代衍生物的高效合成路线将被开发出来。

This project aims for the synthesis and characterization of novel reactive halogenating ionic liquids and their application in the synthesis of new halogenated materials. The halogenating reagents consist of polyhalogen anions with the general formula [F(XF)n]- (with X = Cl, Br, I and n = 1-4). With suitable cations these interhalide salts represent ionic liquids themselves or they are used with ionic liquids as liquefier. Due to the high solubility of gases and the weak interactions with the solute, ionic liquids represent ideal media for the synthesis and application of such polyhalogen monoanions. Furthermore they can be designed to be highly resistant towards strong oxidizers like Cl2, ClF and even elemental fluorine. The polyhalogen monoanions will be prepared by the reaction of naked F- with halogenmonofluorides XF in suitable ionic liquids. Alternatively the reaction of polyhalide salts ([Cat]+[X(X2)n]-, X = Cl, Br, I and n = 1-4) with F2/N2 mixtures will be investigated. Such interhalide salts dissolved in ionic liquids should be versatile halogenating reagents, which are safer and easier to handle than the gaseous, strong oxidizers ClF or F2. Due to their high heat capacity these are good media to moderate the usually quite exothermic halogenation reactions. For the synthesis of new materials we want to use these reactive ionic liquids especially in i) 1,1-addition and 1,2-additions, ii) halogene exchange reactions, and iii) -CN to -CF3 transformation. In particular efficient synthetic routes to the highly desired weakly coordinating closo-borate and closo-carborate anions like [B12X12]2-, [CB11X12]- (X = F, Cl, Br, I) and the corresponding trifluoromethyl-substituted derivatives will be developed.