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首页> 外文期刊>Chemistry: A European journal >Chemistry of bridging phosphanes: Pd-I dimers bearing 2,5-dipyridylphosphole ligands
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Chemistry of bridging phosphanes: Pd-I dimers bearing 2,5-dipyridylphosphole ligands

机译：桥接膦的化学：带有2,5-二吡啶基磷酰基配体的Pd-1二聚体

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摘要

Two synthetic routes to Pd-I dimers that feature a bridging 1-phenyl- and 1-cyclohexyl-2,5-di(2-pyridyl)-phosphole ligand, 3a and 3b, respectively, are described. The first involves a conproportionation process between Pd-II and Pd-0 complexes, while the second involves ligand displacement from a preformed Pd-I dimer. Both routes are operable for 1-phenylphosphole 1a, whereas the former failed with 1-cyclohexylphosphole 1b. A mechanistic study revealed that the conproportionation pathway implies a reversible oxidative addition of the P-C(phenyl) bond of Pd-II-coordinated 1a to Pd-II leading to a bimetallic Pd-II complex 5. The structures of complexes 3a and 3b were studied by means of X-ray diffraction. The similarity of these solid-state structures suggests that the bridging mode of the P atom is due to mu-1kappaN:1,2kappaP:2kappaN coordination of ligands 1a, b. The electrochemical behaviour and UV/Vis absorption properties of complexes 3a, b are reported. Complex 3a is inert towards CO, PPh3 and 1,3-dipoles. It reacted with dimethylacetylene dicarboxylate to give complex 6 as a result of insertion of the alkyne into the Pd-Pd bond. X-ray diffraction studies of complexes 5 and 6 are also presented. [References: 75]
机译：描述了两种分别具有桥连的1-苯基-和1-环己基-2,5-二（2-吡啶基）-磷脂配体3a和3b的Pd-1二聚体的合成途径。第一个涉及Pd-II和Pd-0配合物之间的共配过程，而第二个涉及从预先形成的Pd-I二聚体置换配体。两种途径都可用于1-苯基磷脂1a，而前者以1-环己基磷脂1b失败。机理研究表明，该配位途径意味着将Pd-II配位的1a的PC（苯基）键可逆氧化加成Pd-II，从而形成双金属Pd-II配合物5。研究了配合物3a和3b的结构。通过X射线衍射。这些固态结构的相似性表明，P原子的桥联模式是由于配体1a，b的mu-1kappaN：1,2kappaP：2kappaN配位所致。报道了配合物3a，b的电化学行为和UV / Vis吸收特性。配合物3a对CO，PPh3和1,3-偶极是惰性的。由于炔烃插入Pd-Pd键中，它与二羧酸二甲基乙炔酯反应生成配合物6。还介绍了配合物5和6的X射线衍射研究。 [参考：75]

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