Synthesis of beta-P,N aminophosphines and coordination chemistry to Pd(II). X-ray structures of [PdCl2(Ph2PCH(Ph)NHPh-kappaP,kappaN)] and PdCl(eta3-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)].
The reaction of the C=N bond in PhCH=NPh with the carbanionic species Ph2PCH2-, leading to the N-phenyl beta-aminophosphine Ph2PCH2CH(Ph)NHPh, L1, is described. This molecule reacts with different organic electrophiles to afford related compounds Ph2PCH2CH(Ph)NPhX (X = SiMe3, L2; COPh, L4), [Ph2MePCH2CH(Ph)NHPh]+(I-), L3, and [Ph2PCH2CH(Ph)N(Ph)CO]2, L5, containing two amido and two phosphino functions. The coordination properties of L1, L2, and L4 have been studied in palladium chemistry. The X-ray structure of [PdCl2(Ph2PCH2CH(Ph)NHPh-kappaP,kappaN)] shows the bidentate coordination mode for the L1 ligand with equatorial C(Ph)-N(Ph) phenyl groups. [PdCl2(Ph2PCH2CH(Ph)NHPh-kappaP,kappaN)] crystallizes at 298 K in the space group P2(1)/n with cell parameters a = 10.689(2) A, b = 21.345(3) A, c = 12.282(2) A, beta = 90.294(12) degrees, Z = 4, D(calcd) = 1.526. The reaction between 2 equiv of L1 and [PdCl(eta3-C3H5)]2 affords the [PdCl(eta3-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)] complex in which an unexpected N-H.Cl intramolecular interaction has been observed by an X-ray diffraction analysis. [PdCl(eta3-C3H5)(Ph2PCH2CH(Ph)NHPh-kappaP)] crystallizes at 298 K in the monoclinic space group Cc with cell parameters a = 10.912(1) A, b = 17.194(2) A, c = 14.169(2) A, beta = 100.651(9) degrees, Z = 4, D(calcd) = 1.435. Neutral and cationic alkyl or allyl palladium chloride complexes containing L1 are also reported as well as a neutral allyl palladium chloride complex containing L4. Variable-temperature 31P[1H] NMR studies on the allyl complexes show that the eta3/eta1 allyl interconversion is enhanced by a positive charge and also by a N-H.Cl intramolecular interaction.
Laboratoire de Synthèse et d'Electrosynthèse Organométalliques, Université de Bourgogne, Faculté des Sciences Gabriel, 6, Boulevard Gabriel, 21000 Dijon, France. Jacques.Andrieu@u-bourgogne.fr
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