The reaction of trialkylamine bis(trifluoromethyl)boranes (F 3 C) 2 R 1 B.NR 3 with strong bases has been studied. (F 3 C) 2 EtB.NMe 3 forms a nitrogen ylid when treated with tBuLi, whereas (F 3 C) 2 (NCCH 2 )B.NMe 3 eliminates trimethylamine spontaneously with KOH/ether to form the hydroxyborate K[(F 3 C) 2 (NCCH 2 )BOH] (1a). (F 3 C) 2 (NCCH 2 )B.NMe 3 reacts with tBuLi/thf or PhLi/thf to yield Li[(F 3 C) 2 (NCCH 2 )BtBu] (1b') or Li[(F 3 C) 2 (NCCH 2 )BPh] (1c'), but in the presence of CH 3 CN reaction with tBuLi/thf leads to formation of Li[(F 3 C) 2 (NCCH 2 ) 2 B] (1d'). The lithium salts 1b'-1d' were converted to the corresponding Cs salts 1b-1d using a cation-exchange resin. The tertiary nitrogen of trans-H 3 C-CH CH-CH(CN)(F 3 C) 2 B.NHMe 2 (2) was methylated with KOH/CH 3 I/ether to form trans-H 3 C-CH CH-CH(CN)(F 3 C) 2 B.NMe 3 which further reacted with KOH to form the hydroxyborate K[trans-H 3 C-CH CH-CH(CN)(F 3 C) 2 BOH] (3). BuLi, tBuLi or PhLi cleave the B-N bond of cyclo-(F 3 C) 2 B-CH(CN)-CH 2 -CH 2 -NMe 2 , and subsequent protonation yields the zwitterions R-B(CF 3 ) 2 -CH(CN)-CH 2 -CH 2 -NHMe 2 (R=Bu (4a), tBu (4b) and Ph (4c)). Zwitterions with R=C 3 H 7 C≡C (4d) or PhC≡C (4e) are formed by the reaction of 3 with tBuLi in the presence of C 3 H 7 C≡CH or PhC≡CH. BrCH(CN)(F 3 C) 2 B.NHMe 2 (5), which has been obtained from (F 3 C) 2 BNMe 2 and BrCH 2 CN, forms on treatment with LiOHxH 2 O/ether HOB(CF 3 ) 2 -CH(CN)-NHMe 2 (6). The structure of 6 has been investigated by single-crystal X-ray diffraction.