Phosphorus as Lone Pair Donor and Ligand Acceptor: A Paddlewheel with Ru←P Axis
Phosphorus as Lone Pair Donor and Ligand Acceptor: A Paddlewheel with Ru←P Axis
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DOI：
10.1002/ejic.201701386
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发表时间：
2018-01-10
影响因子：
2.3
通讯作者：
Wagler, Joerg
中科院分区：
文献类型：
--
作者：
Gericke, Robert;Wagler, Joerg
[Ru（PyO）（2）（nbd）]（1）（PyO = 2-吡啶氧基，nbd =降冰片二烯）与PhP（PyO）（2）反应生成配合物[PhP（mu-PyO）（3）Ru（-PyO）]（2），其特征在于五配位的P原子和六配位的Ru原子之间的Ru-P键，由三个PyO配体桥接。CO的加入导致Ru（kappa-PyO）螯合物打开，形成配合物[PhP（mu-PyO）（4）Ru（CO）]（3），这是一种桨轮状配合物，在六配位的P原子和六配位的Ru原子之间具有Ru-P键，由四个PyO配体桥接。在配合物2和3中，P原子充当朝向Ru的孤对施主。有趣的是，P原子还充当配体受体，从而提高其配位数并在Ru处产生配位位点。这些配合物进行了研究，多核NMR光谱，循环伏安法，量子化学计算（NBO/NLMO分析）。
[Ru(PyO)(2)(nbd)] (1) (PyO = 2-pyridyloxy, nbd = norbornadiene) and PhP(PyO)(2) react with formation of complex [PhP(mu-PyO)(3)Ru(-PyO)] (2), which features a Ru-P bond between a pentacoordinate P atom and a hexacoordinate Ru atom, bridged by three PyO ligands. Addition of CO leads to opening of the Ru(kappa-PyO) chelate with formation of complex [PhP(mu-PyO)(4)Ru(CO)] (3), a paddlewheel-shaped complex with a Ru-P bond between a hexacoordinate P atom and a hexacoordinate Ru atom, bridged by four PyO ligands. In complexes 2 and 3 the P atom serves as a lone pair donor toward Ru. Interestingly, the P atom also serves as a ligand acceptor, thus enhancing its coordination number and generating a coordination site at Ru. These complexes were studied by multinuclear NMR spectroscopy, cyclic voltammetry, and quantum chemical calculations (NBO/NLMO analyses).