Phosphoramidate‐Supported Cp*IrIII Aminoborane H2B=NR2 Complexes: Synthesis, Structure, and Solution Dynamics. Issue 20 (31st March 2016)

• Record Type: Journal Article
• Authors: Drover, Marcus W.; Bowes, Eric G.; Schafer, Laurel L.; Love, Jennifer A.; Weller, Andrew S.
• Is Part Of: Chemistry. Volume 22:Issue 20(2016)
• Page Start: 6793
• Page End: 6797
• Publication Date: 2016-03-31
• Subjects: aminoboranes -- B−H activation -- density functional calculations -- iridium -- ligand effects; Chemistry -- Periodicals; 540
• DOI: 10.1002/chem.201600951
• Languages: English
• ISSNs: 0947-6539

Abstract

Abstract: Reaction of aminoboranes H2 B=NR2 (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 NR2 )(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. Abstract : Rotation for DumBNies : Free B−N bond rotation has been observed in a Cp*Ir III aminoborane phosphoramidate complex. Solution‐ and solid‐state techniques, as well as density functional theory, have been employed to substantiate the titled complexes as monohydride mono(BH) agostic Ir III complexes, culminating from phosphoramidate stabilization and B−H activation.