Abstract

A series of L₂ = diimine (Bian = bis(3,5-diisopropylphenylimino)acenapthene, Bu^t₂bpy = 4,4′-di-tert-butyl-2,2′-bipyridine) supported aqua, hydroxo, oxo, amido, imido, and mixed complexes have been prepared. Deprotonation of [L₂Pt(μ-OH)]₂²⁺ with 1,8-bis(dimethylamino)naphthalene, NaH, or KOH yields [(L₂Pt)₂(μ-OH)(μ-O)]⁺ as purple (Bian) or red (Bu^t₂bpy) solids. Excess KOH gives dark blue [(Bian)Pt(μ-O)]₂. MeOTf addition to [(Bu^t₂bpy)₂Pt₂(μ-OH)(μ-O)]⁺ gives [(Bu^t₂bpy)₂Pt₂(μ-OH)(μ-OMe)]²⁺ while [(Bian)Pt(μ-O)]₂ yields [(Bian)₂Pt₂(μ-OMe)(μ-O)]⁺. Treatment of [(Bian)Pt(μ-O)]₂ with “(Ph₃P)Au⁺” gives deep purple [(Bian)₂Pt₂(μ-O)(μ-OAuPPh₃)]⁺ while (COD)Pt(OTf)₂ gives a low yield of [(Bian)Pt₃(μ-OH)₃(COD)₂](OTf)₃. Ni(Bu^t₂bpy)Cl₂ and [(Ph₃PAu)₃(μ-O)]⁺ in a 3 : 2 ratio yield red [Ni₃(Bu^t₂bpy)₃(μ-O)₂]²⁺. M(Bu^t₂bpy)Cl₂ (M = Pd, Pt) and [(Ph₃PAu)₃(μ-O)]⁺ give [M(Bu^t₂bpy)(μ-OauPPh₃)]₂²⁺ and [Pd₄(Bu^t₂bpy)₄(μ-OAuPPh₃)]³⁺. Addition of ArNH₂ to [M(Bu^t₂bpy)(μ-OH)]₂²⁺ (M = Pd, Pt) gives [Pt₂(Bu^t₂bpy)₂(μ-NHAr)(μ-OH)]²⁺ (Ar = Ph, 4-tol, 4-C₆H₄NO₂) and [M(Bu^t₂bpy)(μ-NHAr)]₂²⁺ (Ar = Ph, tol). Deprotonation of [Pt₂(Bu^t₂bpy)₂(μ-NH-tol)(μ-OH)]²⁺ with 1,8-bis(dimethylamino)naphthalene or NaH gives [Pt₂(Bu^t₂bpy)₂(μ-NH-tol)(μ-O)]⁺. Deprotonation of [Pt(Bu^t₂bpy)(μ-NH-tol)]₂²⁺ with KOBu^t gives deep green [Pt(Bu^t₂bpy)(μ-N-tol)]₂. The triflate complexes M(Bu^t₂bpy)(OTf)₂ (M = Pd, Pt) are obtained from M(Bu^t₂bpy)Cl₂ and AgOTf. Treatment of Pt(Bu^t₂bpy)(OTf)₂ with water gives the aqua complex [Pt(Bu^t₂bpy)(H₂O)₂](OTf)₂.

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