Synthesis and characterization of click-decahydrodecaborate derivatives by the copper(I) catalyzed [3+2] azide-alkyne cycloaddition reaction

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

“…The facile and rapid method developed through an efficient click synthetic approach gave access to a large number of novel triaxle‐decaborate coupled derivatives where 1,2,3‐triazole was grafted on the decaborate anion [B 10 H 10 ] 2− [40c,56] . It is based on the nucleophilic cleavage of 2‐tetrahydrofuranium decaborate via sodium azide to form [2‐B 10 H 9 O(CH 2 ) 4 N 3 ] 2− which reacts with various linear alkynes via the copper(I) catalyzed [3+2] azide‐alkyne cycloaddition reaction (Cauca) and therefore forms click‐decaborate derivatives (Scheme 14).…”

Focus on Chemistry of the 10-Dioxane-nido-7,8-dicarba-undecahydrido Undecaborate Zwitterion; Exceptionally Easy Abstraction of Hydrogen Bridge and Double-Action Pathways Observed in Ring Cleavage Reactions with OH− as Nucleophile

“…(see the crystallographic discussion below; crystallographic data are given in the Materials Section and Supplementary Information). 2, O1 C15 1.490(2), O1 B10 1.518(3), B10 B6 1.771(3), B10 B5 1.771(3), B10 B9 1.778(3), B10 B11 1.855(4), O2 C13 1.419(3), O2 C14 1.420(3), B11 C7 1.623(4), B11 B6 1.798(4), B11 B2 1.811(4), C7 C8 1.552(3), C7 B2 1.705(4), C7 B3 1.718(4), B9 C8 1.606(3), B9 B5 1.767(4), B9 B4 1.784(4), C8 B4 1.725(4), C8 B3 1.731(3), B6 B2 1.763(4), B6 B1 1.794(4), B6 B5 1.811(4), B3 B2 1.760(4), B3 B4 1.763(4), B3 B1 1.774(4), B2 B1 1.753(4), C12 O1 C15 110.86 (15), C12 O1 B10 115.64 (15), C15 O1 B10 118.60 (15), O1 B10 B6 116.41 (16), O1 B10 B5 115.16 (17), B6 B10 B5 61.48 (15), O1 B10 B9 124.11 (18), B6 B10 B9 107.75 (17), B5 B10 B9 59.72 (14), O1 B10 B11 125.94 (18), B6 B10 B11 59.40 (14), B5 B10 B11 107.75 (17), B9 B10 B11 105. 10(17).…”

“…This compound belongs to a large and rapidly growing family of species that contain an ether ring attached to the boron cage via an oxonium atom [9][10][11][12]. All other members are derived from closo-borate ions such as cobalt bis(dicarbollide) [13,14], decaborate [15,16], dodecaborate [17][18][19], or 1-carba-undecahydroundecaborate [20]; most of which have been used in numerous emerging applications, among others, advanced materials [21,22], organic conducting polymers [23,24], radionuclide partitioning [25,26], biology, and medicine [8,[27][28][29][30][31][32][33][34][35][36][37]. Surprisingly enough, the nidosystem from this family of compounds, namely compound 1, has largely remained outside the stream of main interest, despite its potential for the introduction of open-cage boron polyhedra to functional molecules and materials.…”

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

“…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 (NH4)2[B10H10] by exploiting the in situ NH4 + counter cation during the nucleophilic addition of nitriles to the borate cluster via Electrophilic-Induced Nucleophilic Substitution mechanism [44,45].…”