Platinum and Palladium Imido and Oxo Complexes with Small Natural Bite Angle Diphosphine Ligands

Treatment of L2MCl2 (M = Pt, Pd; L2 = Ph2PCMe2PPh2 (dppip), Ph2PNMePPh2 (dppma)) with AgX (X = OTf, BF4,
NO3) in wet CH2Cl2 yields the dinuclear dihydroxo complexes [L2M(μ-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(μ-NHAr)]2(BF4)2, the mononuclear
amine complexes [L2M(NH2Ar)2](X)2, or the dinuclear amido−hydroxo complex [Pt2(μ-OH)(μ-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(μ-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 amido−hydroxo complex gives the imido−oxo
complex [Pt2(μ-O)(μ-NAr)(dppip)2]·LiBF4·LiN(SiMe3)2, and deprotonation of the dppip Pt hydroxo complex gives
the dioxo complex [Pt(μ-O)(dppip)]2·LiN(SiMe3)2·2LiBF4.