Diboron (B2pin2) has been identified as an efficient and environmentally benign reducing reagent for reductive coupling reactions for the first time, which enables the nickel-catalyzed reductive tetramerization of alkynes to be performed with high efficiency. Mechanistic and kinetic studies indicate that the facile reductive elimination to form the B-B bond from the dinuclear Ni-Ni complexes is responsible for the high efficiency. The activation enthalpy (ΔH(‡) = 56.5 kJ mol(-1)), entropy (ΔS(‡) = -128 J mol(-1) K(-1)) and the substituent effect (ρ = 1.43) on this reaction were obtained.
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