Phosphoramidate‐Supported Cp*Ir III Aminoborane H 2 B=NR 2 Complexes: Synthesis, Structure, and Solution Dynamics

Reaction of aminoboranes H 2 B=NR 2 (R= i Pr or Cy) with the cationic Cp*Ir III phosphoramidate complex [IrCp*{κ 2 ‐N,O‐Xyl( N )P( O )(OEt) 2 }][BAr F 4 ] generates the aminoborane complexes [IrCp*(H){κ 1 ‐ N ‐η 2 ‐HB‐Xyl( N )P(OB H NR 2 )(OEt) 2 }][BAr F 4 ] (R= i Pr or Cy) in which coordination of a P=O bond with boron weakens the B=N multiple bond. For these complexes, solution‐ and solid‐state, as well as DFT computational techniques, have been employed to substantiate B−N bond rotation of the coordinated aminoborane.