二亚胺支持的第10族羟基、氧代、氨基和亚氨基配合物。

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

作者信息

Singh Anupam, Anandhi U, Cinellu Maria Agostina, Sharp Paul R

机构信息

125 Chemistry, University of Missouri, Columbia, Missouri 65211, USA.

出版信息

Dalton Trans. 2008 May 7(17):2314-27. doi: 10.1039/b715663d. Epub 2008 Mar 4.

DOI:10.1039/b715663d

PMID:18414757

Abstract

A series of L(2) = diimine (Bian = bis(3,5-diisopropylphenylimino)acenapthene, Bu(t)(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridine) supported aqua, hydroxo, oxo, amido, imido, and mixed complexes have been prepared. Deprotonation of L(2)Pt(mu-OH)(2+) with 1,8-bis(dimethylamino)naphthalene, NaH, or KOH yields (L(2)Pt)(2)(mu-OH)(mu-O) as purple (Bian) or red (Bu(t)(2)bpy) solids. Excess KOH gives dark blue (Bian)Pt(mu-O). MeOTf addition to (Bu(t)(2)bpy)(2)Pt(2)(mu-OH)(mu-O) gives (Bu(t)(2)bpy)(2)Pt(2)(mu-OH)(mu-OMe) while (Bian)Pt(mu-O) yields (Bian)(2)Pt(2)(mu-OMe)(mu-O). Treatment of (Bian)Pt(mu-O) with "(Ph(3)P)Au(+)" gives deep purple (Bian)(2)Pt(2)(mu-O)(mu-OAuPPh(3)) while (COD)Pt(OTf)(2) gives a low yield of (Bian)Pt(3)(mu-OH)(3)(COD)(2)(3). Ni(Bu(t)(2)bpy)Cl(2) and (Ph(3)PAu)(3)(mu-O) in a 3 : 2 ratio yield red Ni(3)(Bu(t)(2)bpy)(3)(mu-O)(2). M(Bu(t)(2)bpy)Cl(2) (M = Pd, Pt) and (Ph(3)PAu)(3)(mu-O) give M(Bu(t)(2)bpy)(mu-OAuPPh(3))(2+) and Pd(4)(Bu(t)(2)bpy)(4)(mu-OAuPPh(3)). Addition of ArNH(2) to M(Bu(t)(2)bpy)(mu-OH)(2+) (M = Pd, Pt) gives Pt(2)(Bu(t)(2)bpy)(2)(mu-NHAr)(mu-OH) (Ar = Ph, 4-tol, 4-C(6)H(4)NO(2)) and M(Bu(t)(2)bpy)(mu-NHAr)(2+) (Ar = Ph, tol). Deprotonation of Pt(2)(Bu(t)(2)bpy)(2)(mu-NH-tol)(mu-OH) with 1,8-bis(dimethylamino)naphthalene or NaH gives Pt(2)(Bu(t)(2)bpy)(2)(mu-NH-tol)(mu-O). Deprotonation of Pt(Bu(t)(2)bpy)(mu-NH-tol)(2+) with KOBu(t) gives deep green Pt(Bu(t)(2)bpy)(mu-N-tol). The triflate complexes M(Bu(t)(2)bpy)(OTf)(2) (M = Pd, Pt) are obtained from M(Bu(t)(2)bpy)Cl(2) and AgOTf. Treatment of Pt(Bu(t)(2)bpy)(OTf)(2) with water gives the aqua complex Pt(Bu(t)(2)bpy)(H(2)O)(2)(2).

摘要

已制备出一系列L(2)=二亚胺（Bian=双(3,5-二异丙基苯基亚氨基)苊，Bu(t)(2)bpy=4,4'-二叔丁基-2,2'-联吡啶）负载的水合、羟基、氧代、氨基、亚氨基和混合配合物。用1,8-双（二甲氨基）萘、NaH或KOH使L(2)Pt(μ-OH)(2+)去质子化，得到紫色（Bian）或红色（Bu(t)(2)bpy）固体(L(2)Pt)(2)(μ-OH)(μ-O)。过量的KOH生成深蓝色的(Bian)Pt(μ-O)。向(Bu(t)(2)bpy)(2)Pt(2)(μ-OH)(μ-O)中加入MeOTf得到(Bu(t)(2)bpy)(2)Pt(2)(μ-OH)(μ-OMe)，而(Bian)Pt(μ-O)生成(Bian)(2)Pt(2)(μ-OMe)(μ-O)。用“(Ph(3)P)Au(+)”处理(Bian)Pt(μ-O)得到深紫色的(Bian)(2)Pt(2)(μ-O)(μ-OAuPPh(3))，而(COD)Pt(OTf)(2)以低产率得到(Bian)Pt(3)(μ-OH)(3)(COD)(2)(3)。Ni(Bu(t)(2)bpy)Cl(2)和(Ph(3)PAu)(3)(μ-O)以3:2的比例生成红色的Ni(3)(Bu(t)(2)bpy)(3)(μ-O)(2)。M(Bu(t)(2)bpy)Cl(2)（M=Pd、Pt）和(Ph(3)PAu)(3)(μ-O)生成M(Bu(t)(2)bpy)(μ-OAuPPh(3))(2+)和Pd(4)(Bu(t)(2)bpy)(4)(μ-OAuPPh(3))。向M(Bu(t)(2)bpy)(μ-OH)(2+)（M=Pd、Pt）中加入ArNH(2)得到Pt(2)(Bu(t)(2)bpy)(2)(μ-NHAr)(μ-OH)（Ar=Ph、4-甲苯基、4-C(6)H(4)NO(2)）和M(Bu(t)(2)bpy)(μ-NHAr)(2+)（Ar=Ph、甲苯基）。用1,8-双（二甲氨基）萘或NaH使Pt(2)(Bu(t)(2)bpy)(2)(μ-NH-甲苯基)(μ-OH)去质子化得到Pt(2)(Bu(t)(2)bpy)(2)(μ-NH-甲苯基)(μ-O)。用叔丁醇钾使Pt(Bu(t)(2)bpy)(μ-NH-甲苯基)(2+)去质子化得到深绿色的Pt(Bu(t)(2)bpy)(μ-N-甲苯基)。三氟甲磺酸酯配合物M(Bu(t)(2)bpy)(OTf)(2)（M=Pd、Pt）由M(Bu(t)(2)bpy)Cl(2)和AgOTf制得。用水处理Pt(Bu(t)(2)bpy)(OTf)(2)得到水合配合物Pt(Bu(t)(2)bpy)(H(2)O)(2)(2)。