Nucleophilic Addition Reaction of Secondary Amines to Acetonitrilium closo-Decaborate [2-B10H9NCCH3]–

Synthesis of Boronated Amidines by Addition of Amines to Nitrilium Derivative of Cobalt Bis(Dicarbollide)

“…Of particular interest are the reactions of nitriles with amines in the presence of transition metal complexes, which can be used both in a stoichiometric ratio to study the reactions of coordinated nitriles [31,32], and in catalytic amounts in organic synthesis [69][70][71]. Synthesis of boronated amidines by the reaction of nucleophilic addition of amines to alkylnitrilium derivatives was first described for arachno-decaborate [72] and closo-decaborate [40,41,[73][74][75][76] anions. Later, amidines on the base of nido-carborane [77][78][79] and the closo-dodecaborate anion [80] were synthesized.…”

“…Nucleophilic addition reactions to the highly polarized -N + ≡CR triple bonds in aryl-and alkylnitrilium salts [30] and nitrile complexes of transition metals [31][32][33][34][35] are widely used in organic synthesis and have large potential in the modification of polyhedral boron hydrides [36]. Thus, the nitrilium derivatives of the closo-decaborate anion react with water [37,38], alcohols [39], amines [40,41], hydrazines [42], hydrazones [42] and oximes [43,44], as well as with various carbanions [45,46] to form the corresponding addition products. Like organic nitrilium salts, they are able to participate in 1,3-dipolar cycloaddition reactions with azides and nitrones leading to the corresponding boronated tetrazoles [47] and 2,3-dihydro-1,2,4-oxadiazoles [48], respectively.…”

Recent Achievements on Functionalization within closo‐Decahydrodecaborate [B10H10]2− Clusters

“…Indeed, the significance and versatility of the nitrile group becomes evident during further functionalization of the ‐R group on the cluster [33] . Under mild conditions, the reaction of alcohols with [2‐B 10 H 9 NCCH 3 ] − anion proceeds by the nucleophilic addition mechanism of primary, secondary, and tertiary aliphatic alcohols to produce adducts in quantitative yield.…”

Electrochemical Properties of the closo-Decaborate Anion [B10H10]2– and a New Method for Preparation of the [B20H18]2– Anion

“…The most common approach is electrophilic-induced nucleophilic substitution processes. Based on this approach, it is possible to obtain derivatives of the closo-borate anion with the B-O, B-N, and B-S exo-polyhedral bonds [24,25].…”