Push-pull alkenes bearing closo-decaborate cluster generated via nucleophilic addition of carbanions to borylated nitrilium salts

Abstract Malonodinitrile, benzoylacetonitrile, and ethyl benzoylacetate were deprotonated in situ by n BuLi to give the reactive carbanions R 2 R 3 HC (−) (R 2 /R 3  = CN/CN, CN/COPh, CO 2 Et/COPh), which nucleophilically attack the C N bond of the nitrilium clusters (Ph 4 P)[B 10 H 9 NCR 1 ] (R 1  = Me, Et). This reaction results in generation of push-pull alkenes bearing closo -decaborate clusters, [B 10 H 9 NHC(R 1 ) CR 2 R 3 ] 2− (6 examples; up to 97% isolated yields). These species were isolated as the bis-tetraphenylposhphonium salts and were characterized by 1 H and 11 B NMR, HR ESI +/− -MS, and also by single-crystal X-ray diffraction.