Over the past several decades, metal-catalyzed cross-coupling has emerged as a very powerful strategy to functionalize carbon-based molecules. More recently, some of the cross-coupling methodologies have been adapted to inorganic compounds including boron-rich clusters. The development of this chemistry relies on the ability to synthesize halogenated boron-rich clusters which can serve as electrophilic cross-coupling partners with nucleophilic substrates in the presence of a metal catalyst. While the cross-coupling chemistry with boron-clusters is conceptually reminiscent of that of its hydrocarbon counterparts, several key aspects including the spheroidal bulk of clusters and the distinct nature of boron-halogen/boron-heteroatom bonds make this chemistry unique. The utility of metal-catalyzed cross-coupling can be extended to several classes of polyhedral boranes including neutral and anionic carboranes, metallaboranes, and carbon-free boranes. Importantly, cross-coupling enables a suite of boron-heteroatom (C, N, O, P, S) couplings to prepare boron cluster-based systems that can be used for ligand design, medicinal chemistry, and materials applications.

The chloride gradient plays an important role in regulating cell volume, membrane potential, pH, secretion, and the reversal potential of inhibitory glycine and GABA_A receptors. Measurement of intracellular chloride activity, [Formula: see text], using liquid membrane ion-selective microelectrodes (ISM), however, has been limited by the physiochemical properties of Cl^- ionophores which have caused poor stability, drift, sluggish response times, and interference from other biologically relevant anions. Most importantly, intracellular [Formula: see text] may be up to 4 times more abundant than Cl^- (e.g. skeletal muscle) which places severe constraints on the required selectivity of a Cl^- - sensing ISM. Previously, a sensitive and highly-selective Cl^- sensor was developed in a polymeric membrane electrode using a trinuclear Hg(II) complex containing carborane-based ligands, [9]-mercuracarborand-3, or MC3 for short. Here, we have adapted the use of the MC3 anion carrier in a liquid membrane ion-selective microelectrode and show the MC3-ISM has a linear Nernstian response over a wide range of a_Cl (0.1 mM to 100 mM), is highly selective for Cl^- over other biological anions or inhibitors of Cl^- transport, and has a 10% to 90% settling  time of 3  sec. Importantly, over the physiological range of a_Cl (1 mM to 100 mM) the potentiometric response of the MC3-ISM is insensitive to [Formula: see text] or changes in pH. Finally, we demonstrate the biological application of an MC3-ISM by measuring intracellular a_Cl, and the response to an external Cl-free challenge, for an isolated skeletal muscle fiber.

Off-cycle processes in catalytic reactions can dramatically influence the outcome of the chemical transformation and affect its yield, selectivity, rate, and product distribution. While the generation of off-cycle intermediates can complicate reaction coordinate analyses or hamper catalytic efficiency, the generation of such species may also open new routes to unique chemical products. Recently, we reported the Pd-mediated functionalization of carboranes with a range of O-, N-, and C-based nucleophiles. By utilizing a Pd-based catalytic system supported by a biaryl phosphine ligand developed by Buchwald and co-workers, we discovered an off-cycle isomerization process ("cage-walking") that generates four regioisomeric products from a single halogenated boron cluster isomer. Here we describe how several off-cycle processes affect the regioisomer yield and distribution during Pd-catalyzed tandem cage-walking/cross-coupling. In particular, tuning the transmetallation step in the catalytic cycle allowed us to incorporate the cage-walking process into Pd-catalyzed cross-coupling of sterically unencumbered substrates, including cyanide. This work demonstrates the feasibility of using tandem cage-walking/cross-coupling as a unique low-temperature method for producing regioisomers of mono-substituted carboranes.

In contrast to the plethora of metal-catalyzed cross-coupling methods available for the installation of functional groups on aromatic hydrocarbons, a comparable variety of methods are currently not available for icosahedral carboranes, which are boron-rich three-dimensional aromatic analogues of aryl groups. Part of this is due to the limited understanding of the elementary steps for cross-coupling involving carboranes. Here, we report our efforts in isolating metal-boryl complexes to further our understanding of one of these elementary steps, oxidative addition. Structurally characterized examples of group 10 M-B bonds featuring icosahedral carboranes are completely unknown. Use of mercurocarboranes as a reagent to deliver M-B bonds saw divergent reactivity for platinum and palladium, with a Pt-B bond being isolated for the former, and a rare Pd-Hg bond being formed for the latter.

The chloride gradient plays an important role in regulating cell volume, membrane potential, pH, secretion, and the reversal potential of inhibitory glycine and GABA_A receptors. Measurement of intracellular chloride activity, [Formula: see text], using liquid membrane ion-selective microelectrodes (ISM), however, has been limited by the physiochemical properties of Cl^- ionophores which have caused poor stability, drift, sluggish response times, and interference from other biologically relevant anions. Most importantly, intracellular [Formula: see text] may be up to 4 times more abundant than Cl^- (e.g. skeletal muscle) which places severe constraints on the required selectivity of a Cl^- - sensing ISM. Previously, a sensitive and highly-selective Cl^- sensor was developed in a polymeric membrane electrode using a trinuclear Hg(II) complex containing carborane-based ligands, [9]-mercuracarborand-3, or MC3 for short. Here, we have adapted the use of the MC3 anion carrier in a liquid membrane ion-selective microelectrode and show the MC3-ISM has a linear Nernstian response over a wide range of a_Cl (0.1 mM to 100 mM), is highly selective for Cl^- over other biological anions or inhibitors of Cl^- transport, and has a 10% to 90% settling  time of 3  sec. Importantly, over the physiological range of a_Cl (1 mM to 100 mM) the potentiometric response of the MC3-ISM is insensitive to [Formula: see text] or changes in pH. Finally, we demonstrate the biological application of an MC3-ISM by measuring intracellular a_Cl, and the response to an external Cl-free challenge, for an isolated skeletal muscle fiber.

Carboranes are boron-rich molecules that can be functionalized through metal-catalyzed cross-coupling. Here, for the first time, we report the use of bromo-carboranes in palladium-catalyzed cross-coupling for efficient B-N, B-O, and unprecedented B-CN bond formation. In many cases bromo-carboranes outperform the traditionally utilized iodo-carborane species. This marked difference in reactivity is leveraged to circumvent multistep functionalization by directly coupling small nucleophiles (-OH, -NH2, and -CN) and multiple functional groups onto the boron-rich clusters.

Self-assembled monolayers (SAMs) of carborane isomers with different dipole moments passivate germanium to modulate surface work function while maintaining chemical environment and surface energy. To identify head groups capable of monolayer formation on germanium surfaces, we studied thiol-, hydroxyl-, and carboxyl-terminated carboranes. These films were successfully formed with carboxylic acid head groups instead of the archetypal thiol, suggesting that the carborane cluster significantly affects headgroup reactivity. Film characterization included X-ray and ultraviolet photoelectron spectroscopies as well as contact angle goniometry. Using these carboranes, the germanium surface work function was tailored over 0.4 eV without significant changes to wetting properties.