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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Synthesis and characterization of palladium (II) complexes with a novel chelating iminocarbene ligand
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Synthesis and characterization of palladium (II) complexes with a novel chelating iminocarbene ligand

机译：新型螯合亚氨基卡宾配体的钯（II）配合物的合成与表征

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The reaction between 1-chloro-2-(2,6-diisopropylphenylimino) propane and N-nethylimidazole yelds 3-methyl-1-{2-(2,6-diisopropylphenylimino) propyl}imidazolium] chloride,(C-N)·HCl(2).A silver (I) iminocarbene complex formualted as (C-N)_2Ag~+AgCl_2~- is formed in the reaction between 2 and Ag_2O.Carbene transfer to Pd occurs when 2 is treated with (COD)Pd(Cl)(X) to yield (C-N)Pd(Cl)(X)(4a,X=Cl;4b,X=CH_3).Chloride abstraction from 4a and 4b with AgPF_6 in MeCN yields (C-N)Pd(NCMe)(X)~+PF_6~- (5a and 5n).A second chloride abstraction can be done with 5a to yield (C-N)Pd(NCMe)_2~(2+)(PF_6~-)_2 (6).An X-ray structure determination of 4a verifies the chelating nature of the iminocarbene ligand system and shows that the molecule adopts a boat conformatio nwith Pd and the CH_2 link between the carbene and the imine occupying the two apical positions.The species 4-6 have been subjected to extensive analysis by variable-temperature,EXSY,and NOESY NMR spectroscopy in various solvents.In the weakly coordianting solvent nitromethane,4a and 4b exist as square planar species in which the iminocarbene acts as a C,N-chelating ligand.NMR experiments reveal a dynamic behavior of 4a that involves a boat "flip".This process is fast even at -40 deg C for 4b but considerably slower for 4a.In more coordinating solvents,evidence is seen for solvent-dependent equilibra that involve rapid interconversion between the chelating kappa~2(C,N) structures (kappa~2-(C-N))Pd(Cl)(X) and non-chelating kappa~1(C) iminocarbene structures (kappa~1-(C-N))Pd(Cl)(X)(Solvent).Complex 5a exists as two interconverting species,possibly cis/trans isomers by interchange of the MeCN and Cl ligands,whereas no evidence for dynamic processes is seen for 5b and 6.
机译：1-氯-2-（2,6-二异丙基苯基亚氨基）丙烷与N-乙基咪唑的反应生成3-甲基-1- {2-（2,6-二异丙基苯基亚氨基）丙基}咪唑鎓]氯化物，（CN）·HCl（ 2）。在2与Ag_2O之间的反应中形成了形式为（CN）_2Ag〜+ AgCl_2〜-的亚氨基银（I）络合物。当用（COD）Pd（Cl）（X）处理2时，碳会向Pd转移）得到（CN）Pd（Cl）（X）（4a，X = Cl; 4b，X = CH_3）.MeCN中用AgPF_6从4a和4b中提取氯化物得到（CN）Pd（NCMe）（X）〜+ PF_6〜-（5a和5n）。可以用5a进行第二次氯化物提取，得到（CN）Pd（NCMe）_2〜（2 +）（PF_6〜-）_ 2（6）。图4a验证了亚氨基卡宾配体系统的螯合性质，表明该分子采用与Pd呈舟状构象，并且卡宾与亚胺之间的CH_2连接占据了两个顶端位置。对物种4-6进行了广泛的可变分析。溶剂中的高温，EXSY和NOESY NMR光谱y配位溶剂硝基甲烷4a和4b以方形平面形式存在，其中亚氨基卡宾充当C，N螯合配体。NMR实验表明4a的动态行为涉及船的“翻转”。 40b时4b的温度较慢，但​​4a则相当慢。在更多配位溶剂中，证据表明存在溶剂依赖性平衡基，涉及螯合kappa〜2（C，N）结构（kappa〜2-（CN））Pd之间的快速相互转化（Cl）（X）和非螯合的kappa〜1（C）亚氨基卡宾结构（kappa〜1-（CN））Pd（Cl）（X）（溶剂）。络合物5a作为两个互变物种存在，可能是顺式/反式MeCN和Cl配体互换得到的异构体，而没有发现5b和6有动态过程的证据。

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