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

A series of L-2 = diimine (Bian = bis(3,5-diisopropylphenylimino) acenapthene, Bu(2)(t)bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) supported aqua, hydroxo, oxo, amido, imido, and mixed complexes have been prepared. Deprotonation of [L2Pt(mu-OH)](2)(2+) with 1,8-bis(dimethylamino) naphthalene, NaH, or KOH yields [(L2Pt)(2)(mu-OH)(mu-O)](+) as purple (Bian) or red (Bu(2)(t)bpy) solids. Excess KOH gives dark blue [(Bian)Pt(mu-O)](2). MeOTf addition to [(Bu(2)(t)bpy)(2)Pt-2(mu-OH)(mu-O)](+) gives [(Bu(2)(t)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 (Ph3P)Au+ gives deep purple [(Bian)(2)Pt-2(mu-O)(mu-OAuPPh3)](+) while (COD)Pt(OTf)(2) gives a low yield of [(Bian)Pt-3(mu-OH)(3)(COD)(2)](OTf)(3). Ni(Bu(2)(t)bpy)Cl-2 and [(Ph3PAu)(3)(mu-O)](+) in a 3 : 2 ratio yield red [Ni-3(Bu(2)(t)bpy)(3)(mu-O)(2)](2+). M(Bu(2)(t)bpy)Cl-2 (M = Pd, Pt) and [(Ph3PAu)(3)(mu-O)](+) give [M(Bu(2)(t)bpy)(mu-OAuPPh3)](2)(2+) and [Pd-4(Bu(2)(t)bpy)(4)(mu-OAuPPh3)](3+). Addition of ArNH2 to [M(Bu(2)(t)bpy)(mu-OH)](2)(2+) (M = Pd, Pt) gives [Pt-2(Bu(2)(t)bpy)(2)(mu-NHAr)(mu-OH)](2+) (Ar = Ph, 4-tol, 4-C6H4NO2) and [M(Bu(2)(t)bpy)(mu-NHAr)](2)(2+) (Ar = Ph, tol). Deprotonation of [Pt-2(Bu(2)(t)bpy)(2)(mu-NH-tol)(mu-OH)](2+) with 1,8-bis(dimethylamino) naphthalene or NaH gives [Pt-2(Bu(2)(t)bpy)(2)(mu-NH-tol)(mu-O)](+). Deprotonation of [Pt(Bu(2)(t)bpy)(mu-NH-tol)](2)(2+) with KOBut gives deep green [Pt(Bu(2)(t)bpy)(mu-N-tol)](2). The triflate complexes M(Bu(2)(t)bpy)(OTf)(2) (M = Pd, Pt) are obtained from M(Bu(2)(t)bpy)Cl-2 and AgOTf. Treatment of Pt(Bu(2)(t)bpy)(OTf)(2) with water gives the aqua complex [Pt(Bu(2)(t)bpy)(H2O)(2)](OTf)(2).