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1,3‐N,O‐chelated complexes of RhI and IrI 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...
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