99511-26-9Relevant academic research and scientific papers
Synthesis of new hybrid phosphine amide complexes of rhodium(I) and iridium(I). Intramolecular chelate-assisted oxidative addition of an N-H bond to iridium(I)
Hedden, David,Roundhill, D. Max
, p. 9 - 15 (2008/10/08)
The hybrid phosphine amide ligands o-Ph2PC6H4NHC(O)Ph (PNH(CPhO)) and o-Ph2PC6H4C(O)NHPh (P(CO)NHPh)) react with [MCl(1,5-COD)]2 to give the monomeric complexes MCl(1,5-COD)PNH(CPhO)) and MCl(1,5-COD)(P(CO)NHPh) (M = Rh, Ir). The complexes are 4-coordinate with a P-bonded monodentate phosphine amide ligand. P,N-Chelate complexes [M(1,5-COD)(PN(CPh(OH)))]ClO4 and [M(1,5-COD)(P(COH)NPh)]ClO4 (M = Rh, Ir) are formed by the addition of 1 equiv of the ligand to [M(1,5-COD)(THF)2]ClO4. The complexes are proposed to have the hybrid ligand coordinated through a nitrogen in the iminoyl form. Solutions of the complexes in acetonitrile solvent undergo intramolecular exchange. For [Rh(1,5-COD)-(PN(CPh(OH)))]+ this pathway involves replacement of the iminoyl by MeCN, but for [Rh(1,5-COD)(P(COH)NPh)]+ the process involves addition of MeCN into the fifth coordination position. In the case where iminoyl substitution occurs, the dangling ligand arm has the amide structure. The complexes RhCl(1,5-COD)(PNH(CPhO)), RhCl(1,5-COD)(P(CO)NHPh), and IrCl(1,5-COD)(P(CO)NHPh) react with base to give respectively Rh(1,5-COD)(PN(CPhO)), Rh(1,5-COD)(P(CO)NPh), and Ir(1,5-COD)(P(CO)NPh).
