Generated in situ from air-stable cobalt precursors or readily synthesized using NaHBEt3, (PPh3)3CoH(N2) was found to be an effective catalyst for the hydroboration of alkenes. Unlike previous base-metal catalysts for alkene isomerization-hydroboration which favor the incorporation of boron at terminal positions, (PPh3)3CoH(N2) promotes boron incorporation adjacent to π-systems even in substrates where the alkene is at a remote position, enabling a unique route to 1,1-diboron compounds from α,ω-dienes.