Diimine supported group 10 hydroxo, oxo, amido, and imido complexes

A series of L(2) = diimine (Bian = bis(3,5-diisopropylphenylimino)acenapthene, Bu(t)(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) supported aqua, hydroxo, oxo, amido, imido, and mixed complexes have been prepared. Deprotonation of L(2)Pt(mu-OH)](2)(2+) with 1,8-bis(dimethylamino)naphthalene, NaH, or KOH yields (L(2)Pt)(2)(mu-OH)(mu-O)](+) as purple (Bian) or red (Bu(t)(2)bpy) solids. Excess KOH gives dark blue (Bian)Pt(mu-O)](2). MeOTf addition to (Bu(t)(2)bpy)(2)Pt(2)(mu-OH)(mu-O)](+) gives (Bu(t)(2)bpy)(2)Pt(2)(mu-OH)(mu-OMe)](2+) while (Bian)Pt(mu-O)](2) yields (Bian)(2)Pt(2)(mu-OMe)(mu-O)](+). Treatment of (Bian)Pt(mu-O)](2) with "(Ph(3)P)Au(+)" gives deep purple (Bian)(2)Pt(2)(mu-O)(mu-OAuPPh(3))](+) while (COD)Pt(OTf)(2) gives a low yield of (Bian)Pt(3)(mu-OH)(3)(COD)(2)](OTf)(3). Ni(Bu(t)(2)bpy)Cl(2) and (Ph(3)PAu)(3)(mu-O)](+) in a 3 : 2 ratio yield red Ni(3)(Bu(t)(2)bpy)(3)(mu-O)(2)](2+). M(Bu(t)(2)bpy)Cl(2) (M = Pd, Pt) and (Ph(3)PAu)(3)(mu-O)](+) give M(Bu(t)(2)bpy)(mu-OAuPPh(3))](2)(2+) and Pd(4)(Bu(t)(2)bpy)(4)(mu-OAuPPh(3))](3+). Addition of ArNH(2) to M(Bu(t)(2)bpy)(mu-OH)](2)(2+) (M = Pd, Pt) gives Pt(2)(Bu(t)(2)bpy)(2)(mu-NHAr)(mu-OH)](2+) (Ar = Ph, 4-tol, 4-C(6)H(4)NO(2)) and M(Bu(t)(2)bpy)(mu-NHAr)](2)(2+) (Ar = Ph, tol). Deprotonation of Pt(2)(Bu(t)(2)bpy)(2)(mu-NH-tol)(mu-OH)](2+) with 1,8-bis(dimethylamino)naphthalene or NaH gives Pt(2)(Bu(t)(2)bpy)(2)(mu-NH-tol)(mu-O)](+). Deprotonation of Pt(Bu(t)(2)bpy)(mu-NH-tol)](2)(2+) with KOBu(t) gives deep green Pt(Bu(t)(2)bpy)(mu-N-tol)](2). The triflate complexes M(Bu(t)(2)bpy)(OTf)(2) (M = Pd, Pt) are obtained from M(Bu(t)(2)bpy)Cl(2) and AgOTf. Treatment of Pt(Bu(t)(2)bpy)(OTf)(2) with water gives the aqua complex Pt(Bu(t)(2)bpy)(H(2)O)(2)](OTf)(2).