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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Symmetrical and unsymmetrical pincer complexes with group 10 metals: Synthesis via aryl C-H activation and some catalytic applications
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Symmetrical and unsymmetrical pincer complexes with group 10 metals: Synthesis via aryl C-H activation and some catalytic applications

机译：具有第10组金属的对称和不对称钳形络合物：通过芳基C-H活化合成和某些催化应用

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摘要

Aryl-based pincer metal complexes with anionic terdentate ligands have been widely applied in organic synthesis, organometallic catalysis and other related areas. Synthetically, the most simple and convenient method for the construction of these complexes is the direct metal-induced C_(aryl)-H bond activation, which can be fulfilled by choosing the appropriate functional donor groups in the two side arms of the aryl-based pincer preligands. In this perspective, we wish to summarize some results achieved by our group in this context. Successful examples include symmetrical chiral bis(imidazoline) NCN pincer complexes with Ni(ii), Pd(ii) and Pt(ii), bis(phosphinite) and bis(phosphoramidite) PCP pincer Pd(ii) complexes, unsymmetrical (pyrazolyl)phosphinite, (amino)phosphinite and (imino)phosphinite PCN pincer Pd(ii) complexes, chiral (imidazolinyl)phosphinite and (imidazolinyl) phosphoramidite PCN pincer complexes with Ni(ii) and Pd(ii) as well as unsymmetrical (oxazolinyl)amine and (oxazolinyl)pyrazole NCN′ pincer Pd(ii) complexes. Among them, the P-donor containing complexes are efficiently synthesized by the "one-pot phosphorylation/metalation" method. The obtained symmetrical and unsymmetrical pincer complexes have been used as catalysts in Suzuki-Miyaura reaction (Pd), asymmetric Friedel-Crafts alkylation of indole with trans-β-nitrostyrene (Pt) as well as in asymmetric allylation of aldehyde and sulfonimine (Pd). In the Suzuki couplings conducted at 40-50 °C, some unsymmetrical Pd complexes exhibit much higher activity than the related symmetrical ones which can be attributed to their faster release of active Pd(0) species resulting from the hemilabile coordination of the ligands. Literature results on the synthesis of some related pincer complexes as well as their activities in the above catalytic reactions are also presented.
机译：具有阴离子型齿状配体的基于芳基的钳金属配合物已广泛应用于有机合成，有机金属催化和其他相关领域。综上，构建这些配合物最简单，最方便的方法是直接金属诱导的C_（芳基）-H键活化，这可以通过在基于芳基的两个侧臂中选择合适的功能性供体基团来实现钳夹配体。从这个角度来看，我们希望总结一下我们小组在这种情况下取​​得的一些成果。成功的例子包括具有Ni（ii），Pd（ii）和Pt（ii）的对称手性双（咪唑啉）NCN钳形配合物，双（次膦酸酯）和双（亚磷酰胺）PCP钳形Pd（ii）配合物，不对称的（吡唑基）次膦酸酯，（氨基）次膦酸酯和（亚氨基）次膦酸酯PCN钳形Pd（ii）配合物，手性（咪唑啉基）次膦酸酯和（亚咪唑啉基）亚磷酰胺PCN钳形配合物与Ni（ii）和Pd（ii）以及不对称的（恶唑啉基）胺和（恶唑啉基）吡唑NCN'钳制Pd（ii）复合物。其中，通过“一锅磷酸化/金属化”方法有效地合成了含P供体的配合物。所获得的对称和不对称钳形配合物已被用作Suzuki-Miyaura反应（Pd），吲哚与反式-β-硝基苯乙烯（Pt）的不对称Friedel-Crafts烷基化反应以及醛和亚磺胺（Pd）的不对称烯丙基化反应的催化剂。在40-50°C下进行的Suzuki偶联中，一些不对称的Pd配合物比相关的对称配合物显示出更高的活性，这可以归因于它们由于配体的半不稳定配位而导致活性Pd（0）物种更快地释放。还提供了有关一些相关钳式配合物的合成及其在上述催化反应中的活性的文献结果。

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