Sun Xiong, Shen Jinghang, Rajeshkumar Thayalan, Maron Laurent, Zhu Congqing
State Key Laboratory of Coordination Chemistry, Jiangsu Key Laboratory of Advanced Organic Materials, School of Chemistry and Chemical Engineering, Nanjing University, Nanjing 210023, China.
School of Environmental Engineering, Wuxi University, Wuxi 214105, China.
Inorg Chem. 2023 Oct 2;62(39):16077-16083. doi: 10.1021/acs.inorgchem.3c02259. Epub 2023 Sep 21.
Ligands are known to play a crucial role in the construction of complexes with metal-metal bonds. Compared with metal-metal bonds involving d-block transition metals, knowledge of the metal-metal bonds involving f-block rare-earth metals still lags far behind. Herein, we report a series of complexes with cerium-transition-metal bonds, which are supported by two kinds of nitrogen-phosphorus ligands N[CHCHNHPPr] () and PyNHCHPPh (). The reactions of zerovalent group 10 metal precursors, Pd(PPh) and Pt(PPh), with the cerium complex supported by generate heterometallic clusters [N{CHCHNPPr}Ce(μ-M)] (M = Pd, and M = Pt, ) featuring four Ce-M bonds; meanwhile, the bimetallic species [(PyNCHPPh)Ce-M] (M = Ni, ; M = Pd, ; and M = Pt, ) with a single Ce-M bond were isolated from the reactions of the cerium precursor supported by with Ni(COD), Pd(PPh), or Pt(PPh), respectively. These complexes represent the first example of species with an RE-M bond between Ce and group 10 metals, and and contain the largest number of RE-M donor/acceptor interactions ever to have been observed in a molecule.
已知配体在构建具有金属-金属键的配合物中起着关键作用。与涉及d区过渡金属的金属-金属键相比，关于涉及f区稀土金属的金属-金属键的知识仍然远远落后。在此，我们报道了一系列具有铈-过渡金属键的配合物，它们由两种氮磷配体N[CHCHNHPPr] () 和PyNHCHPPh () 支撑。零价第10族金属前体Pd(PPh) 和Pt(PPh) 与由 支撑的铈配合物反应，生成具有四个Ce-M键的异金属簇[N{CHCHNPPr}Ce(μ-M)] (M = Pd, 且M = Pt, )；同时，分别从由 支撑的铈前体 与Ni(COD)、Pd(PPh) 或Pt(PPh) 的反应中分离出具有单个Ce-M键的双金属物种[(PyNCHPPh)Ce-M] (M = Ni, ; M = Pd, ; 且M = Pt, )。这些配合物代表了在铈与第10族金属之间具有RE-M键的物种的首个实例，并且 和 包含了在一个分子中观察到的数量最多的RE-M供体/受体相互作用。
