Synthesis of beta-P,N aminophosphines and coordination chemistry to Pd-II.X-ray structures of [Pd Cl-2(Ph2PCH2CH(Ph)NHPh- kP,kN)] and [PdCl(eta(3)-C3H5) (Ph2PCH2CH(Ph)NHPh-kP)]

The reaction of the C=N bond in PhCH=NPh with the carbanionic species Ph2PC H2-, leading to the N-phenyl beta -aminsphosphine Ph2PCH2CH(Ph)NHPh, L-1, i s described. This molecule reacts with different organic electrophiles to a fford related compounds Ph2PCH2CH(Ph)NPhX (X = SiMe3, L-2; COPh, L-4), [Ph2 MePCH2CH(Ph)NHPh](+)(I-), L-3, and [Ph2PCH2CH(Ph)N(Ph)CO](2), L-5, containi ng two amido and two phosphino functions. The coordination properties of L- 1, L-2, and L-4 have been studied in palladium chemistry. The X-ray structu re of [PdCl2(Ph2PCH2-CH(Ph)NHPh-kappaP,kappaN)I shows the bidentate coordin ation mode for the L-1 Ligand with equatorial C-Ph-N-Ph phenyl groups. [PdC l2(Ph2PCH2CH(Ph)NHPh-kappaP,kappaN)] crystallizes at 298 K in the space gro up P2(1)/n with cell parameters a = 10.689(2) Angstrom, b = 21.345(3) Angst rom, c = 12.282(2) Angstrom, beta = 90.294(1.2)degrees Z = 4, D-calcd = 1.5 26. The reaction between 2 equiv of L-1 and [PdCl(eta (3)-C3H5)](2) affords the [PdCl(eta (3)-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)] complex in which an une xpected N-H . . . Cl intramolecular interaction has been observed by an X-r ay diffraction analysis. [PdCl(eta (3)-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)] cry stallizes at 298 K in the monoclinic space group Cc with cell parameters a = 10.912(1) Angstrom, b = 17.194(2) Angstrom, c = 14.169(2) Angstrom, beta = 100.651(9)degrees Z = 4, D-calcd = 1.435. Neutral and cationic alkyl or a llyl palladium chloride complexes containing L-1 are also reported as well as a neutral allyl palladium chloride complex containing L-4. Variable-temp erature P-31{H-1} NMR studies on the allyl complexes show that the eta (3)/ eta (1) allyl interconversion is enhanced by a positive charge and also by a N-H . . . Cl intramolecular interaction.