Polymers and ceramics based on icosahedral carboranes. Model studies of the formation and hydrolytic stability of aryl ether, ketone, amide and borane linkages between carborane units

Dicarba‐closo‐dodecaboranes with One and Two Ethynyl Groups Bonded to Boron

“…DFT-GIAO [58] NMR spectroscopic shielding constants σ( 11 B), σ( 13 C), and σ( 1 H) as well as spin-spin coupling constants [59] were calculated at the B3LYP/6-311++G(2d,p) level of theory using the geometries computed at the B3LYP/6-311++G(d,p) level of theory. The 11 B, 13 C, and 1 H NMR spectroscopic shielding constants were calibrated to the respective chemical shift scale δ( 11 B), δ( 13 C), and δ( 1 H) using predictions on diborane (6) and Me 4 Si with chemical shifts of -16.6 ppm for B 2 H 6 [60] and 0 ppm for Me 4 Si. [61] All calculations were carried out with the Gaussian 03 program suite.…”

“…On account of their potential uses as building blocks for a wide range of applications, for example, in supramolecular chemistry, [1,2] pharmaceuticals, [3,4] and dendrimers [5] or polymers, [6] the functionalization of the three isomeric icosahedral dicarba-closo-dodecaboranes (Scheme 1) has been studied extensively. [7,8] This includes the incorporation of functional groups at the carbon vertices that may be achieved by deprotonation and subsequent reaction with an electrophile, as well as the modification of the substituents at the boron vertices (e.g., by electrophilic halogenation or alkylation).…”

Spontaneous vs. Base‐Induced Dehydrochlorination of Group 14 ortho‐Carboranylamidinates

“…[5][6][7] With R = ortho-C 2 H 11 B 10 , ("ortho-carboranyl"), we introduced another chemically versatile moiety into the backbone of the amidinate ligand. Since their discovery in the 1960s, [8] carboranes have gained a continuously rising interest as regards various applications, including the synthesis of polymers and ceramics, [9] catalysts, [10][11][12] radiopharmaceuticals, [13] and nonlinear optics. [14] The new ligand type of ortho-carboranylamidinates was first synthesized in our laboratory in 2010 by in situ lithiation of the parent carborane, ortho-C 2 H 12 B 10 (= orthodicarba-closo-dodecaborane), followed by treatment with an equivalent amount of a carbodiimide (Scheme 1).…”

Reactivity differences between nickel and palladium complexes bearing 1,2-diphosphino-1,2-dicarba-dodecaborane ligand

“…Transition metal complexes containing carborane ligands were shown to have potential applications in many areas, such as boron neutron capture treatment (BNCT) of tumor [1,2], photophysical properties [3,4], polymers for high temperature [5], anticancer treatment [6], supramolecular chemistry, etc [7e11]. The most intensively studied substituted carboranes are 1,2-dichalocogenolato-1,2-dicarbadodecaborane dianions [E 2 C 2 (B 10 H 10 )] 2À (E ¼ S, Se) [12e18] and 1,2-diphosphino-1,2-dicarba-dodecaborane ligands [(PR 2 ) 2 (C 2 B 10 H 10 )] (R ¼ phenyl, isopropyl, etc.)…”