Capturing HBCy2: Using N,O‐Chelated Complexes of Rhodium(I) and Iridium(I) for Chemoselective Hydroboration

1,3-N,O-chelated complexes of Rh(I) and Ir(I) cooperatively and reversibly stabilized the B-H bond of HBCy2 to afford six-membered metallaheterocycles (M=Rh (7) or Ir (8)) having a δ-[M]⋅⋅⋅H-B agostic interaction. Treatment of these Shimoi-type borane adducts 7 or 8 with both an aldehyde and an alkene resulted in chemoselective aldehyde hydroboration and reformation of the 1,3-N,O-chelated starting material. The observed chemoselectivity is inverted from that of free HBCy2 , which is selective for alkene hydroboration.