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The synthesis and structural characterization of the first sulfur-containing derivatives of C,C-biscarborane {ortho-C2B10}2 cluster – thiol, thioether, and disulfide- is reported. The biscarboranyl dithiol (1-HS-C2B10H10)2 exhibits the exceedingly long intracluster carbon-carbon bond length of 1.858(3) Å, which is attributed to the extensive interaction between lone pairs of thiol groups and the unoccupied molecular orbital of carborane cluster. The structures of doubly deprotonated biscarboranyl dithiolate anion (1-S-C2B10H10)22– with various countercations feature even longer carbon-carbon bond of 2.062(10) Å within the cluster along with the short carbon-sulfur bond of 1.660(7) Å, both indicative of significant delocalization of electron density from sulfur atoms into the cluster.more » « less
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Icosahedral closo -dodecaboranes have the ability to accept two electrons, opening into a dianionic nido -cluster. This transformation can be utilized to store electrons, drive bond activation, or alter coordination to metal cations. In this feature article, we present cases for each of these applications, wherein the redox activity of carborane facilitates the generation of unique products. We highlight the effects of exohedral substituents on reactivity and the stability of the products through conjugation between the cluster and exohedral substituents. Futher, the utilization of the redox properties and geometry of carborane clusters in the ligand design is detailed, both in the stabilization of low-valent complexes and in the tuning of ligand geometry.more » « less
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We report the synthesis and characterization of a nickel(II) complex of the dicarboranyl CNC dianionic pincer ligand, which activates acetonitrile by C–C bond cleavage. Deprotonation of the relatively acidic C–H bond of the coordinated acetonitrile with potassium t-butoxide led to the formation of the C-bound cyanomethylene ligand at the metal center. Unlike most previously characterized Ni(II) cyanoalkyls, the resulting complex exhibited quick transformation under aerobic conditions at room temperature to afford CNC-ligated nickel(II) cyanide, indicating facile cleavage of the C–CN bond. The cyanoalkyl and cyanide complexes were isolated in excellent yields and characterized by NMR spectroscopy and single-crystal X-ray diffraction. Carbon-containing products of the aerobic C–CN bond activation are hydroxyacetonitrile, formaldehyde, cyanomethyl formate, and carbon dioxide.more » « less
