Platinum and palladium imido and oxo complexes with small natural bite angle diphosphine ligands

Treatment of L2MCl2 (M = Pt, Pd; L-2 = Ph2PCMe2PPh2 (dppip), Ph2PNMePPh2 (dppma)) with AgX (X = OTf, BF4, NO3) in wet CH2Cl2 yields the dinuclear dihydroxo complexes [L2M(mu-OH)](2)(X)(2), the mononuclear aqua complexes [L2M(OH2)(2)](X)(2), the mononuclear anion complexes L2MX2, or mixtures of complexes. Addition of aromatic amines to these complexes or mixtures gives the dinuclear diamido complexes [L2Pt(mu-NHAr)](2)(BF4)(2), the mononuclear amine complexes [L2M(NH2Ar)(2)](X)(2), or the dinuclear amido-hydroxo complex [Pt-2(mu-OH)(mu-NHAr)(dppip)(2)](BF4)(2), Deprotonation of the Pd and Pt amine or diamido complexes with M'N(SiMe3)(2) (M' = Li, Na, K) gives the diimido complexes [L2M(mu-NAr)](2) associated with M' salts. Structural studies of the Li derivatives indicate association through coordination of the imido nitrogen atoms to Li+. Deprotonation of the amiclo-hydroxo complex gives the imido-oxo complex [Pt-2(mu-O)(mu-NAr)(dppip)(2)].LiBF4-LiN(SiMe3)(2), and deprotonation of the dppip Pt hydroxo complex gives the dioxo complex [Pt(mu-O)(dppip)](2)-LiN(SiMe3)(2).2LiBF(4).