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            A new class of stable four-coordinated benzotriazole-borane compounds was developed via gold-catalyzed alkyne hydroboration. The application of polymeric (BH 2 CN) n reagent gave the formation of cyano-amine-boranes (CAB) complexes with less basic N-heterocyclic amines and anilines. Various new CABs were investigated in catalytic hydroboration to synthesize N–B cycles. The 1,2,3-benzotriazoles were identified as the only feasible N-source, giving the four coordinated borane N–B cycles (BTAB) in excellent yields (up to 90%) with good functional group tolerability. This new class of polycyclic N–B compounds showed excellent stability toward acid, base, high temperature, and photo-irradiation. The facile synthesis, excellent stability, strong and tunable fluorescence emission make BTAB interesting new fluorescent probes for future chemical and biological applications.more » « less
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            Abstract Silanes are important in chemistry and material science. The self‐redistribution of HSiCl3is an industrial process to prepare SiH4, which is widely used in electronics and automobile industries. However, selective silane cross‐redistribution to prepare advanced silanes is challenging. We now report an enthalpy‐driven silane cross‐redistribution to access bis‐silanes that contain two different types of Si−H bonds in the same molecule. Compared with entropy‐driven reactions, the enthalpy‐driven reaction shows high regioselectivity, broad substrate scope (62 examples) and high atom economy. Our combined experimental and computational study indicates that the reaction proceeds through a Ni0‐NiII‐NiIVcatalytic cycle.more » « less
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