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(Dimethylamino)bis(trifluoromethyl)borane, (CF3)2BNMe2 (1), combines with N-sulfinylsulfonamides RO2SNSO in a [2 + 2] fashion (R = Me (2a), Et (2b), iPr (2c), Ph (2d), and pTol (2e)). Aminoiminophosphines RNPNR2‘ react with 1 analogously to yield the = SiMe3, NR2‘ = N(SiMe3)2 (3a), TMP (3b); R = tBu, NR2‘ = N(SiMe3)tBu (3c), NiPr2 (3d), TMP (3e)). Carbodiimides RNCNR add to the BN bond of 1 to give unstable which rearrange at 20 °C to yield the four-membered heterocycles = iPr (5a), cC6H11 (5b)). For carbodiimides with aryl substituents R = pXC6H4, this rearrangement competes with an internal electrophilic aromatic substitution reaction and mixtures of the two (X = H (5c), Me (5d), OMe (5e)) (X = H (6c), Me (6d), OMe (6e)) are obtained. PhNCCMe2 combines with 1 to form the four-membered F3C−CH2−NSO undergoes an ene-type reaction with 1 by which the dimethylamine borane (F3CHCNS(O))(CF3)2B·NHMe2 (9) is formed. The constitution of the novel boron compounds has been deduced from multinuclear NMR, IR, and mass spectra. The structures of 2a, 3c, 5c, 6d, 6e, and 8 have been investigated by single-crystal X-ray diffraction.

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