Clean-activation of the B–H bond in closo-decahydrodecaborate [B10H10]2− anion via soft-route

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

“…A more recent method of synthesis was reported via the clean‐activation of the B−H bond in closo‐decaborate anion where its starting ammonium salt (NH 4 ) 2 [B 10 H 10 ] was refluxed in distilled acetonitrile to afford the mono‐substituted [2‐B 10 H 9 NCCH 3 ] − . When this reaction was realized in acetonitrile, the hydrolyzed derivative (NH 4 )[B 10 H 9 NH 2 COCH 3 ] (hydrolysis of CH 3 CN‐ to CH 3 CONH‐) is obtained with 99 % yield [32] …”

“…When this reaction was realized in acetonitrile, the hydrolyzed derivative (NH 4 )[B 10 H 9 NH 2 COCH 3 ] (hydrolysis of CH 3 CN-to CH 3 CONH-) is obtained with 99 % yield. [32] 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 ] À anion proceeds by the nucleo- ChemistrySelect philic addition mechanism of primary, secondary, and tertiary aliphatic alcohols to produce adducts in quantitative yield.…”

Selective Functionalization of Carbonyl Closo-Decaborate [2-B10H9CO]− with Building Block Properties via Grignard Reagents

“…The impedance in the functionalization of the closo -decaborate anion is primarily dictated by the electronic environment of the cage; this can be quite challenging due to the presence of 10 inert B–H bonds in a rather stable and comparable chemical environment; B-H bond substitution can proceed via electrophilic or nucleophilic mechanisms in either apical (boron atoms with a co-ordination number of 4) or equatorial (boron atoms with a co-ordination number of 5) positions to yield mono-, di- and poly-substituted derivatives [ 27 , 30 , 31 , 43 ]. A recent soft approach utilized an auto-catalyzed reaction pathway to functionalize (NH 4 ) 2 [B 10 H 10 ] by exploiting the in situ NH 4 + counter cation during the nucleophilic addition of nitriles to the borate cluster via Electrophilic-Induced Nucleophilic Substitution mechanism [ 44 , 45 ].…”

“…The impedance in the functionalization of the closo-decaborate anion is primarily dictated by the electronic environment of the cage; this can be quite challenging due to the presence of 10 inert B-H bonds in a rather stable and comparable chemical environment; B-H bond substitution can proceed via electrophilic or nucleophilic mechanisms in either apical (boron atoms with a co-ordination number of 4) or equatorial (boron atoms with a co-ordination number of 5) positions to yield mono-, di-and poly-substituted derivatives [27,30,31,43]. A recent soft approach utilized an auto-catalyzed reaction pathway to functionalize (NH 4 ) 2 [B 10 H 10 ] by exploiting the in situ NH 4 + counter cation during the nucleophilic addition of nitriles to the borate cluster via Electrophilic-Induced Nucleophilic Substitution mechanism [44,45]. The impedance in the functionalization of the closo-decaborate anion is primarily dictated by the electronic environment of the cage; this can be quite challenging due to the presence of 10 inert B-H bonds in a rather stable and comparable chemical environment; B-H bond substitution can proceed via electrophilic or nucleophilic mechanisms in either apical (boron atoms with a co-ordination number of 4) or equatorial (boron atoms with a co-ordination number of 5) positions to yield mono-, di-and poly-substituted derivatives [27,30,31,43].…”

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

“…This class of compounds is used as one of the most convenient starting platforms for creating bioinorganic boron-containing platforms. Currently, there are many approaches to the directed functionalization of boron cluster anions [21][22][23]. The most common approach is electrophilic-induced nucleophilic substitution processes.…”