Synthesis of Differently Substituted N- and P-Aminodiphosphinoamine PNPN-H Ligands

Abstract On the basis of the known aminodiphosphinoamine ligand Ph2PN(i-Pr)P(Ph) N(i-Pr)-H (3a), differently substituted aminodiphosphinoamine PNPN-H ligands (3) were prepared. By using different synthetic methods, the N-substituted ligands Ph2PN (i-Pr)P(Ph)N(c-Hex)-H (3b), Ph2PN(c-Hex)P(Ph)N(i-Pr)-H (3g), and Ph2PN(i-Pr)P(Ph) N[(CH2)3Si(OEt)3]-H (3c), in addition to the formerly described Ph2PN(n-Hex)P (Ph)N (i-Pr)-H (3h), Ph2PN(i-Pr)P(Ph)N(Et)-H (3d), Ph2PN(i-Pr)P(Ph)N(Me)-H (3e), and Ph2PN(c-Hex)P(Ph)N(c-Hex)-H (3f), were obtained. In addition, Ph2PN(i-Pr)P(Me)N(i-Pr)-H (3i), (cyclopentyl)2PN(i-Pr)P(Ph)N(i-Pr)-H (3j), (-O-CH2-CH2-O-)PN(i-Pr)P(Ph)N(i-Pr)-H (3k), and (1-Ad)2PN(i-Pr)P(Ph)N(i-Pr)-H (3l) were prepared with different P-substitutions. All compounds were characterized and the molecular structures of the intermediates Ph2PN(i-Pr)P(Ph)Cl (1a) and (cyclopentyl)2PN(i-Pr)P(Ph)Cl (1e) and the ligand (1-Ad)2PN(i-Pr)P(Ph)N(i-Pr)-H (3l) were investigated by single-crystal X-ray diffraction. Supplementa...