Activation of Acetonitrile with (C2F5)(3)PF2 and Amines

作者：Bader Julia; Neumann Beate; Stammler Hans Georg; Ignat'ev Nikolai; Hoge Berthold^*

来源：Chemistry - A European Journal, 2018, 24(27): 6975-6982.

DOI：10.1002/chem.201800682

• gas separation
• hydroamination
• Lewis acids
• nitriles
• phosphorus

Acetonitrile is deprotonated by a combination of the strong Lewis acid (C2F5)(3)PF2 and triethylamine. The resulting cyanomethyl function is bound to the phosphorus moiety, affording the highly stable salt [HNEt3][P(C2F5)(3)F-2(CH2CN)]. Salt metathesis reactions furnished the corresponding [Cu(MeCN)(2)](+) and [Ag(MeCN)](+) derivatives in which the CH2CN substituent of the anion [P(C2F5)(3)F-2(CH2CN)](-) coordinates to the metal. An investigation of the gas separation capability of the silver salt [Ag(MeCN)][P(C2F5)(3)F-2(CH2CN)] shows an uptake of 1.7equivalents of isobutene from a propane/isobutene mixture. The reaction of (C2F5)(3)PF2 with acetonitrile and diethylamine furnishes [P(C2F5)(3)F-2{NHC(CH3)NEt2}]a phosphate featuring an amidine ligand which formally results from hydroamination of acetonitrile by HNEt2. Exchange of HNEt2 with the primary amines H2NPh and H2NBu leads to comparable amidine salts that exhibit a solvent-dependent conformational isomerism.

• 出版日期2018-5-11