Cathodic Cleavage of C-S and C-P in Carboranyl Derivatives

Substituent Effects on the Fluorescence Properties of ortho‐Carbor­anes: Unusual Emission Behaviour in C‐(2′‐Pyridyl)‐ortho‐carboranes

“…S-H bond cleavage follows on reduction of 9 based on the reported [65] electrochemical reduction of thiophenol. Cleavage of the carborane C-S bond occurs in 10 and likewise cleavage of the carborane C-P bond in 11 and 15 on the basis of a CV study [64] on related sulfur and phosphorus carboranes.…”

“…Only three compounds (14, 16 and 17) showed reversible waves (Table S2); therefore, the cathodic wave values for 1 and 4-17 are listed in Table 4 for comparison. It has been shown elsewhere that CV studies of 1, [62] 4, [63] 6, [63] 7 [63] and 12 [64] contain irreversible waves due to either carborane C-H or C-P cleavage, addition of a proton to the dianion formed, spontaneous deboronation of the dianion formed or combinations of these processes. For 4, 11 and 13, cleavage of the carborane C-H bond takes place on reduction.…”

N,O-Type Carborane-Based Materials

“…It was found that an exchange coupling for both Fe III atoms in 31 was strongly antiferromagnetic. 2 under heating conditions (Scheme 13) [58]. Chiral rhodium complexes 32 (chloride form) and 35 (acetate form) were found to be an effective catalyst (1 mol%) for asymmetric conjugate reaction of α,β-unsaturated esters, giving both a high enantiomeric excess (93%-94% ee).…”

“…The icosahedral closo carboranes (dicarba-closo-dodecaboranes; C 2 B 10 H 12 ) are an interesting class of exceptionally stable boron-rich clusters with high thermal and chemical stability, hydrophobicity and acceptor character [1][2][3]. Carborane chemistry has experienced a major surge of interest across a wide spectrum of technologies, fueled by developing applications in diverse areas such as in catalysis, materials science and medicine [1,[4][5][6][7][8][9][10][11].…”

“…Monosubstitution of the carboranes is not trivial because the monolithiation of the o-carborane moiety is complicated by the tendency of the monolithio o-carborane to disproportionate into o-carborane and its dianion [14]. Several strategies Over the years, our group and others have been interested in the synthesis of new carborane-based ligands containing a variety of donor centers (N, P, S, N/C, N/S, N/P, P/C, P/P P/Si, P/S, S/C or S/S donors) and their metal complexes an applications [2,6,[18][19][20][21][22][23][24][25][26][27][28]. Carborane ligands containing N,O donors are scarce in the literature.…”