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4241057 
Journal Article 
Activation of CH3CN with (C2F5)3PF2 and amines 
Bader, J; Neumann, B; Stammler, HG; Ignatiev, N; Hoge, B 
2018 
Yes 
Chemistry: A European Journal
ISSN: 0947-6539
EISSN: 1521-3765 
English 
29488665 
Acetonitrile is deprotonated by a combination of the strong Lewis acid (C2F5)3PF2 and triethylamine. The resulting cyanomethyl function is bound to the phosphorus moiety, affording the highly stable salt [HNEt3][P(C2F5)3F2CH2CN]. Salt metathesis reactions furnished the corresponding [Cu(MeCN)2]+ and [Ag(MeCN)]+ derivatives in which the CH2CN substituent of the anion [P(C2F5)3F2CH2CN]- coordinates to the metal. An investigation of the gas separation capability of the silver salt [Ag(MeCN)][P(C2F5)3F2CH2CN] shows an uptake of 1.7 equivalents of isobutene from a propane/isobutene mixture. The reaction of (C2F5)3PF2 with acetonitrile and diethylamine furnishes [P(C2F5)3F2NHC(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 which exhibit a solvent-dependent conformational isomerism. 
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