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

摘要

A series of L2 = diimine (Bian = bis(3,5-diisopropylphenylimino)acenapthene, Bu~t_2bpy = 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)]2~(2+) with 1,8-bis(dimethylamino)naphthalene, NaH, or KOH yields [(L2Pt)2(μ-OH)(μ-O)]~+ as purple (Bian) or red (Bu~t_2bpy) solids. Excess KOH gives dark blue [(Bian)Pt(μ-O)]2. MeOTf addition to [(Bu~t_2bpy)2Pt2(μ-OH)(μ-O)]~+ gives[(Bu~t_2bpy)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~t_2bpy)Cl2 and [(Ph3PAu)3(μ-O)]~+ in a 3 : 2 ratio yield red [Ni3(Bu~t_2bpy)3(μ-O)2]~(2+). M(Bu~t_2bpy)Cl2 (M = Pd, Pt) and [(Ph3PAu)3(μ-O)]~+ give [M(Bu~t_2bpy)(μ-OAuPPh3)]_2~(2+) and [Pd4(Bu~t_2bpy)4(μ-OAuPPh3)]~(3+). Addition of ArNH2 to [M(Bu~t_2bpy)(μ-OH)]_2~(2+) (M = Pd, Pt) gives [Pt2(Bu~t_2bpy)2(μ-NHAr)(μ-OH)]~(2+) (Ar = Ph, 4-tol, 4-C6H4NO2) and [M(Bu~t_2bpy)(μ-NHAr)]2~(2+) (Ar = Ph, tol). Deprotonation of [Pt2(Bu~t_2bpy)2(μ-NH-tol)(μOH)]~(2+) with 1,8-bis(dimethylamino)naphthalene or NaH gives [Pt2(Bu~t_2bpy)2(μ-NH-tol)(μ-O)]~+. Deprotonation of [Pt(Bu~t_2bpy)(μ-NH-tol)]_2~(2+) with KOBu~t gives deep green [Pt(Bu~t_2bpy)(μ-N-tol)]2. The triflate complexes M(Bu~t_2bpy)(OTf)2 (M = Pd, Pt) are obtained from M(Bu~t_2bpy)Cl2 and AgOTf. Treatment of Pt(Bu~t_2bpy)(OTf)2 with water gives the aqua complex [Pt(Bu~t_2bpy)(H2O)2](OTf)2.