Synthesis and characterization of the bis-cyclometalating ligand 3,3′,5,5′-tetrakis[(dimethylamino)methyl]biphenyl and its use in the preparation of bimetallic M(II), M(IV) (M = Pt, Pd), and mixed-valence Pt(II)-Pt(IV) complexes via a dilithio-derivative.: Crystal structure of the Pd dimer [ClPd{2,6-(Me2NCH2)2C6H2}]2
Synthesis and characterization of the bis-cyclometalating ligand 3,3′,5,5′-tetrakis[(dimethylamino)methyl]biphenyl and its use in the preparation of bimetallic M(II), M(IV) (M = Pt, Pd), and mixed-valence Pt(II)-Pt(IV) complexes via a dilithio-derivative.: Crystal structure of the Pd dimer [ClPd{2,6-(Me2NCH2)2C6H2}]2
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DOI：
10.1021/om970650k
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发表时间：
1998-02-16
期刊：
影响因子：
2.8
通讯作者：
van Koten, G
中科院分区：
文献类型：
--
作者：
Lagunas, MC;Gossage, RA;van Koten, G
潜在的双环金属化配体3，3 '，5，5'-四[（二甲基氨基）甲基联苯]是由3，5-（Me 2NCH 2）（2）C6 H3 Br通过一锅合成法制备的，涉及锂-卤素交换、金属转移和还原消除反应。该配体在联苯基的4和4'位进行选择性的双金属化反应，形成[Li-2{2，6-（Me 2NCH 2）（2）C6 H2}（2）]（n），其是通过双金属转移反应生成双金属化配合物的通用前体。报道了新的同双核铂（Ⅱ）和钯（Ⅱ）配合物[（MeCN）Pt{2，6-（Me_2NCH_2）（2）C_6H_2}-]（2）（CF_3SO_3）（2）和[ClPt{2，6-（Me_2NCH_2）（2）C_6H_2}-]（2）的合成和表征，以及配合物[ClPt{2，6-（Me_2NCH_2）（2）C_6H_2}-]（2）的新合成路线。用单晶X射线衍射法测定了Pd二聚体的固态结构。Cl-2氧化加成到后一种Pt化合物上产生双铂（IV）配合物[Cl 3 Pt {2，6-（Me 2NCH 2）（2）C6 H2）-]（2），其与2当量的Ag（O3 SCF 3）在MeCN溶液中反应形成[（MeCN）Cl 2 Pt {2，6-（Me 2NCH 2）（2）C6 H2}-]（2）（CF 3SO 3）（2）。该配合物也可以通过前Pt-II二聚体与2当量Cl_2IPh反应直接获得。1H-1 NMR光谱研究表明，Pt-II和Pt-IV二聚体在乙腈溶液中的混合物与混合价（Pt-II，Pt-IV）物种[（MeCN）Pt-II{2，6-（Me 2NCH 2）（2）C6 H2-C6 H2（CH 2NMe 2）-2，6}（PtCl 2）-Cl-IV（NCMe）]（CF 3SO 3）（2）平衡，然而，其不能以纯形式分离。Pt-II二聚体与小于或等于1当量的Cl 2 IPh的反应也得到Pt-IV二聚体，沿着有未反应的原料和混合价络合物。一个可逆的双C-C键的形成：已经实现了通过反应的Pt-II二聚体与过量的甲基碘。该过程产生双（arenonium）物质[IPtII{2，6-（Me 2NCH 2）（2）-1-MeC 6 H2}-]（2）（CF 3SO 3）（2），其中由I-Me键断裂衍生的两个Me基团都与芳基环的C-ipso键合。通过核磁共振氢谱确定了单芳环化合物[IPtII{2，6-（Me_2NCH_2）（2）-1-MeC_6H_2-C_6H_2（CH_2NMe_2）（2）-2 '，6'} Pt-II]（CF_3SO_3）（2）为该反应的中间体。
The potentially bis-cyclometalating ligand 3,3',5,5'-tetrakis[(dimethylamino)methyl biphenyl, was prepared from 3,5-(Me2NCH2)(2)C6H3Br in a one-pot synthesis involving lithium-halogen exchange, transmetalation, and reductive-elimination reactions. This ligand undergoes selective dilithiation in the 4 and 4' positions of the biphenyl group to form [Li-2{2,6-(Me2NCH2)(2)C6H2}(2)](n), which is a versatile precursor to bimetallic complexes via a double transmetalation reaction. The syntheses and characterization of the new homobinuclear Pt(II) and Pd(II) compounds, [(MeCN)Pt{2,6-(Me2NCH2)(2)C6H2}-](2)(CF3SO3)(2) and [ClPt{2,6-(Me2NCH2)(2)C6H2}-](2), is reported in addition to a novel synthetic route to the complex [ClPt{2,6-(Me2NCH2)(2)C6H2}-](2). The solid-state structure of Pd dimer was determined by single-crystal X-ray diffraction. Oxidative addition of Cl-2 to the latter Pt compound produced the bis-platinum(IV) complex [Cl3Pt{2,6-(Me2NCH2)(2)C6H2)-](2), which reacts with 2 equiv of Ag(O3SCF3) in MeCN solution to form [(MeCN)Cl2Pt{2,6-(Me2NCH2)(2)C6H2}-](2)(CF3SO3)(2). This complex could also be obtained directly by reaction of the former Pt-II dimer with 2 equiv of Cl2IPh. H-1 NMR spectroscopic studies show that mixtures of the Pt-II and Pt-IV dimers in acetonitrile solution are in equilibrium with a mixed-valence (Pt-II,Pt-IV) species [(MeCN)Pt-II{2,6-(Me2NCH2)(2)C6H2-C6H2(CH2NMe2)-2,6}(PtCl2)-Cl-IV(NCMe)](CF3SO3)(2), which, however, could not be isolated in pure form. The reaction of the Pt-II dimer with less than or equal to 1 equiv of Cl2IPh also gave a Pt-IV dimer, along with unreacted starting material and the mixed-valence complex. A reversible double C-C bond formation:has been achieved by reaction of the Pt-II dimer with excess of methyl iodide. This procedure yields the bis(arenonium) species [IPtII{2,6-(Me2NCH2)(2)-1-MeC6H2}-](2)(CF3SO3)(2) in which both the Me groups derived from I-Me bond cleavage are bound to the C-ipso of the aryl rings. The mono-(arenonium) compound [IPtII{2,6-(Me2NCH2)(2)-1-MeC6H2-C6H2(CH2NMe2)(2)-2',6'}Pt-II](CF3SO3)(2) has been identified as an intermediate in this reaction by 1H NMR spectroscopy.