作者:Anupam Singh、U. Anandhi、Maria Agostina Cinellu、Paul R. Sharp
DOI:10.1039/b715663d
日期:——
A series of L2 = diimine (Bian = bis(3,5-diisopropylphenylimino)acenapthene, But2bpy = 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 (But2bpy) solids. Excess KOH gives dark blue [(Bian)Pt(μ-O)]2. MeOTf addition to [(But2bpy)2Pt2(μ-OH)(μ-O)]+ gives [(But2bpy)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(But2bpy)Cl2 and [(Ph3PAu)3(μ-O)]+ in a 3 : 2 ratio yield red [Ni3(But2bpy)3(μ-O)2]2+. M(But2bpy)Cl2 (M = Pd, Pt) and [(Ph3PAu)3(μ-O)]+ give [M(But2bpy)(μ-OAuPPh3)]22+ and [Pd4(But2bpy)4(μ-OAuPPh3)]3+. Addition of ArNH2 to [M(But2bpy)(μ-OH)]22+ (M = Pd, Pt) gives [Pt2(But2bpy)2(μ-NHAr)(μ-OH)]2+ (Ar = Ph, 4-tol, 4-C6H4NO2) and [M(But2bpy)(μ-NHAr)]22+ (Ar = Ph, tol). Deprotonation of [Pt2(But2bpy)2(μ-NH-tol)(μ-OH)]2+ with 1,8-bis(dimethylamino)naphthalene or NaH gives [Pt2(But2bpy)2(μ-NH-tol)(μ-O)]+. Deprotonation of [Pt(But2bpy)(μ-NH-tol)]22+ with KOBut gives deep green [Pt(But2bpy)(μ-N-tol)]2. The triflate complexes M(But2bpy)(OTf)2 (M = Pd, Pt) are obtained from M(But2bpy)Cl2 and AgOTf. Treatment of Pt(But2bpy)(OTf)2 with water gives the aqua complex [Pt(But2bpy)(H2O)2](OTf)2.
一系列L2(Bian=双(3,5-二异丙基苯亚胺)苊,But2bpy=4,4'-二叔丁基-2,2'-联吡啶)配位的水合、羟基、氧合、氨基、亚氨基以及混合型络合物已被制备。用1,8-双(二甲基氨基)萘、NaH或KOH去质子化 [L2Pt(μ-OH)]22+ 得到紫色(Bian)或红色(But2bpy)固体 [(L2Pt)2(μ-OH)(μ-O)]+。过量KOH得到深蓝色 [(Bian)Pt(μ-O)]2。将MeOTf加入 [(But2bpy)2Pt2(μ-OH)(μ-O)]+ 得到 [(But2bpy)2Pt2(μ-OH)(μ-OMe)]2+,而 [(Bian)Pt(μ-O)]2 则生成 [(Bian)2Pt2(μ-OMe)(μ-O)]+。用“(Ph3P)Au+”处理 [(Bian)Pt(μ-O)]2 得到深紫色 [(Bian)2Pt2(μ-O)(μ-OAuPPh3)]+,而使用(COD)Pt(OTf)2 则得到低产率的 [(Bian)Pt3(μ-OH)3(COD)2](OTf)3。使用 Ni(But2bpy)Cl2 和 [(Ph3PAu)3(μ-O)]+ 按3:2比例反应生成红色 [Ni3(But2bpy)3(μ-O)2]2+。M(But2bpy)Cl2(M=Pd, Pt)和 [(Ph3PAu)3(μ-O)]+ 生成 [M(But2bpy)(μ-OAuPPh3)]22+ 和 [Pd4(But2bpy)4(μ-OAuPPh3)]3+。向 [M(But2bpy)(μ-OH)]22+(M=Pd, Pt)中加入ArNH2 得到 [Pt2(But2bpy)2(μ-NHAr)(μ-OH)]2+(Ar=Ph, 4-tol, 4-C6H4NO2)和 [M(But2bpy)(μ-NHAr)]22+(Ar=Ph, tol)。用1,8-双(二甲基氨基)萘或NaH去质子化 [Pt2(But2bpy)2(μ-NH-tol)(μ-OH)]2+ 得到 [Pt2(But2bpy)2(μ-NH-tol)(μ-O)]+。使用KOBut去质子化 [Pt(But2bpy)(μ-NH-tol)]22+ 得到深绿色 [Pt(But2bpy)(μ-N-tol)]2。通过M(But2bpy)Cl2和AgOTf反应得到三氟甲磺酸盐络合物 M(But2bpy)(OTf)2(M=Pd, Pt)。处理 Pt(But2bpy)(OTf)2 与水得到水合络合物 [Pt(But2bpy)(H2O)2](OTf)2。