Diimine Supported Group 10 Hydroxo, Oxo, Amido, and Imido Complexes

A series of L2 = diimine (Bian = bis(3,5-diisopropylphenylimino)acenapthene, But 2bpy = 4,4-di-tert-butyl-2,2-bipyridine) supported aqua, hydroxo, oxo, amido, imido, and mixed complexes have been prepared. Deprotonation of [L2Pt(l-OH)]2 2+ with 1,8-bis(dimethylamino)naphthalene, NaH, or KOH yields [(L2Pt)2(l-OH)(l-O)]+ as purple (Bian) or red (But 2bpy) solids. Excess KOH gives dark blue [(Bian)Pt(l-O)]2. MeOTf addition to [(But 2bpy)2Pt2(l-OH)(l-O)]+ gives [(But 2bpy)2Pt2(l-OH)(l-OMe)]2+ while [(Bian)Pt(l-O)]2 yields [(Bian)2Pt2(l-OMe)(l-O)]+. Treatment of [(Bian)Pt(l-O)]2 with “(Ph3P)Au+” gives deep purple [(Bian)2Pt2(l-O)(l-OAuPPh3)]+ while (COD)Pt(OTf)2 gives a low yield of [(Bian)Pt3(l-OH)3(COD)2](OTf)3. Ni(But 2bpy)Cl2 and [(Ph3PAu)3(l-O)]+ in a 3 : 2 ratio yield red [Ni3(But 2bpy)3(l-O)2]2+. M(But 2bpy)Cl2 (M = Pd, Pt) and [(Ph3PAu)3(l-O)]+ give [M(But 2bpy)(l-OAuPPh3)]2 2+ and [Pd4(But 2bpy)4(l-OAuPPh3)]3+. Addition of ArNH2 to [M(But 2bpy)(l-OH)]2 2+ (M = Pd, Pt) gives [Pt2(But 2bpy)2(l-NHAr)(l-OH)]2+ (Ar = Ph, 4-tol, 4-C6H4NO2) and [M(But 2bpy)(l-NHAr)]2 2+ (Ar = Ph, tol). Deprotonation of [Pt2(But 2bpy)2(l-NH-tol)(l-OH)]2+ with 1,8-bis(dimethylamino)naphthalene or NaH gives [Pt2(But 2bpy)2(l-NH-tol)(l-O)]+. Deprotonation of [Pt(But 2bpy)(l-NH-tol)]2 2+ with KOBut gives deep green [Pt(But 2bpy)(l-N-tol)]2. The triflate complexes M(But 2bpy)(OTf)2 (M = Pd, Pt) are obtained from M(But 2bpy)Cl2 and AgOTf. Treatment of Pt(But 2bpy)(OTf)2 with water gives the aqua complex [Pt(But 2bpy)(H2O)2](OTf)2.